U.S. patent application number 10/126041 was filed with the patent office on 2003-04-24 for herbicides comprising benzoylcyclohexanediones and safeners.
Invention is credited to Almsick, Andreas van, Auler, Thomas, Bieringer, Hermann, Hacker, Erwin, Rosinger, Christopher, Willms, Lothar, Ziemer, Frank.
Application Number | 20030078167 10/126041 |
Document ID | / |
Family ID | 7682324 |
Filed Date | 2003-04-24 |
United States Patent
Application |
20030078167 |
Kind Code |
A1 |
Ziemer, Frank ; et
al. |
April 24, 2003 |
Herbicides comprising benzoylcyclohexanediones and safeners
Abstract
Herbicidal compositions are described that comprise active
substances from the group of the benzoylcyclohexanediones and also
safeners. These herbicidal compositions are especially suitable for
use against weed plants in crop plant cultures.
Inventors: |
Ziemer, Frank; (Kriftel,
DE) ; Almsick, Andreas van; (Karben, DE) ;
Willms, Lothar; (Hofheim, DE) ; Auler, Thomas;
(Bad Soden, DE) ; Bieringer, Hermann; (Eppstein,
DE) ; Hacker, Erwin; (Hochhiem, DE) ;
Rosinger, Christopher; (Hofhiem, DE) |
Correspondence
Address: |
FROMMER LAWRENCE & HAUG LLP
745 Fifth Avenue
New York
NY
10151
US
|
Family ID: |
7682324 |
Appl. No.: |
10/126041 |
Filed: |
April 18, 2002 |
Current U.S.
Class: |
504/271 ;
504/294; 504/302; 504/309; 504/326; 504/348 |
Current CPC
Class: |
A01N 43/08 20130101;
A01N 43/80 20130101; A01N 41/10 20130101; A01N 43/80 20130101; A01N
47/30 20130101; A01N 43/80 20130101; A01N 43/76 20130101; A01N
43/56 20130101; A01N 43/42 20130101; A01N 43/28 20130101; A01N
41/06 20130101; A01N 37/10 20130101; A01N 25/32 20130101; A01N
43/08 20130101; A01N 47/30 20130101; A01N 43/80 20130101; A01N
43/76 20130101; A01N 43/56 20130101; A01N 43/42 20130101; A01N
43/28 20130101; A01N 41/06 20130101; A01N 37/10 20130101; A01N
25/32 20130101; A01N 41/10 20130101; A01N 47/30 20130101; A01N
43/80 20130101; A01N 43/76 20130101; A01N 43/56 20130101; A01N
43/42 20130101; A01N 43/28 20130101; A01N 41/06 20130101; A01N
37/10 20130101; A01N 25/32 20130101; A01N 41/10 20130101; A01N
2300/00 20130101; A01N 43/08 20130101; A01N 2300/00 20130101; A01N
43/80 20130101; A01N 2300/00 20130101 |
Class at
Publication: |
504/271 ;
504/302; 504/309; 504/348; 504/294; 504/326 |
International
Class: |
A01N 047/24; A01N
025/00; A01N 043/80; A01N 043/08; A01N 037/34 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 21, 2001 |
DE |
10119721.7 |
Claims
What is claimed is:
1. A herbicidal composition comprising B) a herbicidally effective
amount of one or more compounds of the formula (I) 25in which the
symbols and indices have the following definitions: R.sup.1 is
nitro, amino, halogen, cyano, (C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkynyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.2-C.sub.4)-haloalkenyl,
(C.sub.2-C.sub.4)-haloalkynyl, (C.sub.1-C.sub.4)-haloalkoxy,
(C.sub.1-C.sub.4)-haloalkylthio, (C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-alkylsulfinyl,
(C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alko- xy,
(C.sub.1-C.sub.4)-alkylcarbonyl,
(C.sub.1-C.sub.4)-alkylaminosulfonyl,
(C.sub.1-C.sub.4)-dialkylaminosulfonyl,
(C.sub.1-C.sub.4)-alkylcarbamoyl,
(C.sub.1-C.sub.4)-dialkylcarbamoyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.s- ub.4)-alkyl,
(C.sub.1-C.sub.4)-alkylamino or (C.sub.1-C.sub.4)-dialkylamin- o;
R.sup.2 is (C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)--
alkoxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.3-C.sub.6)-cycloalkoxy-(C.sub.1-C.- sub.4)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.4)-alkoxy,
tetrahydrofuran-2-yl-methoxy-(C.sub.1-C.sub.4)-alkyl,
tetrahydrofuran-3-yl-methoxy-(C.sub.1-C.sub.4)-alkyl or a
heterocyclic radical from the group consisting of isoxazol-3-yl and
4,5-dihydroisoxazol-3-yl which is substituted by a radical from the
group consisting of cyanomethyl, ethoxymethyl and methoxymethyl;
R.sup.3 is OR.sup.5, cyano, halogen, cyanato, thiocyanato,
(C.sub.1-C.sub.4)-alkylth- io, (C.sub.1-C.sub.4)-alkylsulfinyl,
(C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.2-C.sub.4)-alkenylthio,
(C.sub.2-C.sub.4)-alkenylsulfinyl,
(C.sub.2-C.sub.4)-alkenylsulfonyl, (C.sub.2-C.sub.4)-alkynylthio,
(C.sub.2-C.sub.4)-alkynylsulfinyl,
(C.sub.2-C.sub.4)-alkynylsulfonyl, (C.sub.1-C.sub.4)-haloalkylthio,
(C.sub.2-C.sub.4)-haloalkenylthio,
(C.sub.2-C.sub.4)-haloalkynylthio,
(C.sub.1-C.sub.4)-haloalkylsulfinyl,
(C.sub.2-C.sub.4)-haloalkenylsulfinyl,
(C.sub.2-C.sub.4)-haloalkynylsulfi- nyl,
(C.sub.1-C.sub.4)-haloalkylsulfonyl,
(C.sub.2-C.sub.4)-haloalkenylsul- fonyl or
(C.sub.2-C.sub.4)-haloalkynylsulfonyl; R.sup.4 is
(C.sub.1-C.sub.4)-alkyl; R.sup.5 is hydrogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl or
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)- -alkyl; a is 0, 1, 2 or
3; b is 0, 1 or 2; and B) an antidote-active amount of one or more
compounds from groups a) to e): b) compounds of the formula (II) to
(IV), 26in which the symbols and indices have the following
definitions: n' is a natural number from 1 to 5, preferably from 1
to 3; T is a (C.sub.1- or C.sub.2-)-alkanediyl chain which is
unsubstituted or substituted by one or two (C.sub.1-C.sub.4)-alkyl
radicals or by [(C.sub.1-C.sub.3)-alkoxy]carbonyl; W is a radical
from the group (W1) to (W4), 27m' is 0 or 1; R.sup.17, R.sup.19 are
identical or different and are hydrogen, halogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, nitro or
(C.sub.1-C.sub.4)-haloalkyl; R.sup.18 and R.sup.20 are identical or
different and are OR.sup.24, SR.sup.24 or NR.sup.24R.sup.25 or a
saturated or unsaturated 3- to 7-membered heterocycle containing at
least one nitrogen atom and up to 3 heteroatoms which is bonded by
the nitrogen atom to the carbonyl group in (II) or (III) and is
unsubstituted or substituted by radicals from the group consisting
of (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy and
unsubstituted or substituted phenyl, preferably a radical of the
formula OR.sup.24, NHR.sup.25 or N(CH.sub.3).sub.2, in particular
of the formula OR.sup.24; R.sup.24 is hydrogen or an unsubstituted
or substituted aliphatic hydrocarbon radical, preferably having a
total of from 1 to 18 carbon atoms; R.sup.25 is hydrogen,
(C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy or substituted or
unsubstituted phenyl; R.sup.26 is hydrogen,
(C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.8)-haloalkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.6)-hydro- xyalkyl, (C.sub.3-C.sub.12)-cycloalkyl or
tri-(C.sub.1-C.sub.4)-alkylsilyl- ; R.sup.27, R.sup.28 and R.sup.29
are identical or different and are hydrogen,
(C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.6)-haloalkyl,
(C.sub.3-C.sub.12)-cycloalkyl or substituted or unsubstituted
phenyl; R.sup.21 is (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.2-C.sub.4)-alkenyl,
(C.sub.2-C.sub.4)-haloalkenyl, (C.sub.3-C.sub.7)-cycloalkyl,
preferably dichloromethyl; R.sup.22, R.sup.23 are identical or
different and are hydrogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenyl, (C.sub.2-C.sub.4)-alkynyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.2-C.sub.4)-haloalkenyl,
(C.sub.1-C.sub.4)-- alkylcarbamoyl-(C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenylcarbamoy- l-(C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alky- l,
dioxolanyl-(C.sub.1-C.sub.4)-alkyl, thiazolyl, furyl, furylalkyl,
thienyl, piperidyl, substituted or unsubstituted phenyl, or
R.sup.22 and R.sup.23 together form a substituted or unsubstituted
heterocyclic ring, preferably an oxazolidine, thiazolidine,
piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; c)
one or more compounds from the following group: 1,8-naphthalic
anhydride, methyl diphenylmethoxyacetate,
cyanomethoxyimino(phenyl)acetonitrile (cyometrinile),
1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),
4'-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyl
oxime (fluxofenim), 4,6-dichloro-2-phenylpyrimi- dine (fenclorim),
benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxy- late
(flurazole), 2-dichloromethyl-2-methyl-1,3-dioxoiane (MG-191),
N-(4-methylphenyl)-N'-(1-methyl-1-phenylethyl)urea (dymron),
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,
(2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic
acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
(4-chloro-o-tolyloxy)acetic acid (MCPA),
4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)buty- ric
acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba),
1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate
(lactidichlor) and their salts and esters, preferably
(C.sub.1-C.sub.8); c) N-acylsulfonamides of the formula (V) and
their salts, 28in which R.sup.30 is hydrogen, a carbon-containing
radical such as a hydrocarbon radical, a hydrocarbon-oxy radical, a
hydrocarbon-thio radical or a heterocyclyl radical, each of the 4
last-mentioned radicals being unsubstituted or being substituted by
one or more identical or different radicals selected from the group
consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl,
formyl, carboxamide, sulfonamide and radicals of the formula
--Z.sup.a--R.sup.a, each hydrocarbon moiety preferably having 1 to
20 carbon atoms and a carbon-containing radical R.sup.30 inclusive
of substituents preferably having 1 to 30 carbon atoms; R.sup.31 is
hydrogen or (C.sub.1-C.sub.4)-alkyl, preferably hydrogen, or
R.sup.30 and R.sup.31 together with the group of the formula
--CO--N-- are the residue of a 3- to 8-membered saturated or
unsaturated ring; R.sup.32 is identical or different and is
halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl,
CONH.sub.2, SO.sub.2NH.sub.2 or a radical of the formula
--Z.sup.b--R.sup.b; R.sup.33 is hydrogen or
(C.sub.1-C.sub.4)-alkyl, preferably H; R.sup.34 is identical or
different and is halogen, cyano, nitro, amino, hydroxyl, carboxyl,
CHO, CONH.sub.2, SO.sub.2NH.sub.2 or a radical of the formula
--Z.sup.c--R.sup.c; R.sup.a is a hydrocarbon radical or a
heterocyclyl radical, each of the two last-mentioned radicals being
unsubstituted or substituted by one or more identical or different
radicals selected from the group consisting of halogen, cyano,
nitro, amino, hydroxyl, mono- and di-[(C.sub.1-C.sub.4)-a-
lkyl]amino, or an alkyl radical in which a plurality, preferably 2
or 3, non-adjacent CH.sub.2 groups are in each case replaced by one
oxygen atom; R.sup.b,R.sup.c are identical or different and are a
hydrocarbon radical or a heterocyclyl radical, each of the two
last-mentioned radicals being unsubstituted or substituted by one
or more identical or different radicals selected from the group
consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl,
halo-(C.sub.1-C.sub.4)-alkoxy, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino, or an alkyl radical in which a
plurality, preferably 2 or 3, non-adjacent CH.sub.2 groups are
replaced in each case by one oxygen atom; Z.sup.a is a divalent
group of the formula --O, --S, --CO, --CS, --CO--O, --CO--S,
--O--CO, --S--CO, --SO, --SO.sub.2, --NR*, --CO--NR*, --NR*--CO,
--SO.sub.2--NR* or --NR*--SO.sub.2, the bond given on the
right-hand side of each of the divalent groups being the bond to
the radical R.sup.a, and the radicals R* in the 5 last-mentioned
radicals independently of each other being in each case H,
(C.sub.1-C.sub.4)-alkyl or halo-(C.sub.1-C.sub.4)-alkyl;
Z.sup.b,Z.sup.c independently of one another are a direct bond or a
divalent group of the formula --O, --S, --CO, --CS, --CO--O,
--CO--S, --O--CO, --S--CO, --SO, --SO.sub.2, --NR*,
--SO.sub.2--NR*, --NR*--SO.sub.2, --CO--NR* or --NR*--CO, the bond
given on the right-hand side to the radical R.sup.b or R.sup.c and
the radicals R* in the 5 last-mentioned radicals independently of
one another being in each case H, (C.sub.1-C.sub.4)-alkyl or
halo-(C.sub.1-C.sub.4)-alkyl; n is an integer from 0 to 4,
preferably 0, 1 or 2, in particular 0 or 1, and m is an integer
from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; d)
acylsulfamoylbenzamides of the formula (VI), optionally also in
salt form, 29in which X.sup.3 is CH or N; R.sup.35 is hydrogen,
heterocyclyl or a hydrocarbon radical, the two last-mentioned
radicals optionally being substituted by one or more identical or
different radicals selected from the group consisting of halogen,
cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH.sub.2,
SO.sub.2NH.sub.2 and Z.sup.a--R.sup.a; R.sup.36 is hydrogen,
hydroxyl, (C.sub.1-C.sub.6)-alkyl, (C.sub.2-C.sub.6)-alkenyl,
(C.sub.2-C.sub.6)-alkynyl, (C.sub.1-C.sub.6)-alkoxy,
(C.sub.2-C.sub.6)-alkenyloxy, the five last-mentioned radicals
optionally being substituted by one or more identical or different
radicals selected from the group consisting of halogen, hydroxyl,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy and
(C.sub.1-C.sub.4)-alkylthio, or R.sup.35 and R.sup.36 together with
the nitrogen atom to which they are attached are a 3- to 8-membered
saturated or unsaturated ring; R.sup.37 is halogen, cyano, nitro,
amino, hydroxyl, carboxyl, CHO, CONH.sub.2, SO.sub.2NH.sub.2 or
Z.sup.b--R.sup.b; R.sup.38 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenyl or (C.sub.2-C.sub.4)-alkynyl; R.sup.39 is
halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO,
CONH.sub.2, SO.sub.2NH.sub.2 or Z.sup.c--R.sup.c; R.sup.a is a
(C.sub.2-C.sub.20)-alkyl radical whose carbon chain is interrupted
once or more than once by oxygen atoms, or is heterocyclyl or a
hydrocarbon radical, the two last-mentioned radicals optionally
being substituted by one or more identical or different radicals
selected from the group consisting of halogen, cyano, nitro, amino,
hydroxyl, mono- and di-[(C.sub.1-C.sub.4)-alkyl]amino; R.sup.b,
R.sup.c are identical or different and are a
(C.sub.2-C.sub.20)-alkyl radical whose carbon chain is interrupted
once or more than once by oxygen atoms, or a heterocyclyl or a
hydrocarbon radical, the two last-mentioned radicals optionally
being substituted by one or more identical or different radicals
selected from the group consisting of halogen, cyano, nitro, amino,
hydroxyl, phosphoryl, (C.sub.1-C.sub.4)-haloalkoxy, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino- ; Z.sup.a is a divalent unit
selected from the group consisting of O, S, CO, CS, C(O)O, C(O)S,
SO, SO.sub.2, NR.sup.d, C(O)NR.sup.d or SO.sub.2NR.sup.d; Z.sup.b,
Z.sup.c are identical or different and are a direct bond or a
divalent unit selected from the group consisting of O, S, CO, CS,
C(O)O, C(O)S, SO, SO.sub.2, NR.sup.d, SO.sub.2NR.sup.d or
C(O)NR.sup.d; R.sup.d is hydrogen, (C.sub.1-C.sub.4)-alkyl or
(C.sub.1-C.sub.4)-haloalkyl; r is an integer from 0 to 4, and q in
the event that X.sup.3 is CH, is an integer from 0 to 5 and, in the
event that X is N, is an integer from 0 to 4; f) compounds of the
formula (VII), 30in which the symbols and indices have the
following definitions: X is CH or N, p in the event that X=N, is an
integer from 0 to 2 and, in the event that X=CH, is an integer from
0 to 3; R.sup.40 is halogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkoxy, nitro, (C.sub.1-C.sub.4)-alkylthio,
(C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-alkoxycarbonyl,
phenyl or phenoxy, the two last-mentioned radicals being
unsubstituted or substituted by one or more, preferably up to
three, identical or different radicals from the group consisting of
halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.1-C.sub.4)-alkoxy, halo-(C.sub.1-C.sub.4)-alkoxy, nitro and
cyano; R.sup.41 is hydrogen or (C.sub.1-C.sub.4)-alkyl, and
R.sup.42 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl,
(C.sub.2-C.sub.6)-alkynyl or aryl, each of the aforementioned
carbon-containing radicals being unsubstituted or substituted by
one or more, preferably up to three, identical or different
radicals from the group consisting of halogen, nitro, cyano,
hydroxyl, (C.sub.1-C.sub.8)-alkoxy, in which one or more,
preferably up to three, CH.sub.2 groups may be replaced by oxygen,
(C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyloxy and
(C.sub.2-C.sub.4)-alkynyloxy, inclusive of the stereoisomers and
the agriculturally customary salts.
2. The herbicidal composition as claimed in claim 1, comprising
safeners of the formula (II) and/or (III) wherein the symbols and
indices have the following definitions: R.sup.24 is hydrogen,
(C.sub.1-C.sub.18)-alkyl, (C.sub.3-CO.sub.2)-cycloalkyl,
(C.sub.2-C.sub.8)-alkenyl and (C.sub.2-C.sub.8)-alkynyl, where the
carbon-containing groups can be substituted by one or more,
preferably up to three, radicals R.sup.50; R.sup.50 is identical or
different and is halogen, hydroxyl, (C.sub.1-C.sub.8)-alkoxy,
(C.sub.1-C.sub.8)-alkylthio, (C.sub.2-C.sub.8)-alkenylthio,
(C.sub.2-C.sub.8)-alkynylthio, (C.sub.2-C.sub.8)-alkenyloxy,
(C.sub.2-C.sub.8)-alkynyloxy, (C.sub.3-C.sub.7)-cycloalkyl,
(C.sub.3-C.sub.7)-cycloalkoxy, cyano, mono- and
di-(C.sub.1-C.sub.4)-alkyl)amino, carboxyl,
(C.sub.1-C.sub.8)-alkoxyc- arbonyl,
(C.sub.2-C.sub.8)-alkenyloxycarbonyl, (C.sub.1-C.sub.8)-alkylthio-
carbonyl, (C.sub.2-C.sub.8)-alkynyloxycarbonyl,
(C.sub.1-C.sub.8)-alkylcar- bonyl,
(C.sub.2-C.sub.8)-alkenylcarbonyl,
(C.sub.2-C.sub.8)-alkynylcarbony- l,
1-(hydroxyimino)-(C.sub.1-C.sub.6)-alkyl,
1-[(C.sub.1-C.sub.4)-alkylimi- no]-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkoxyimino]-(C.sub.1-C.- sub.6)-alkyl,
(C.sub.1-C.sub.8)-alkylcarbonylamino,
(C.sub.2-C.sub.8)-alkenylcarbonylamino,
(C.sub.2-C.sub.8)-alkynylcarbonyl- amino, aminocarbonyl,
(C.sub.1-C.sub.8)-alkylaminocarbonyl,
di-(C.sub.1-C.sub.6)-alkylaminocarbonyl,
(C.sub.2-C.sub.6)-alkenylaminoca- rbonyl,
(C.sub.2-C.sub.6)-alkynylaminocarbonyl, (C.sub.1-C.sub.8)-alkoxyca-
rbonylamino, (C.sub.1-C.sub.8)-alkylaminocarbonylamino,
(C.sub.1-C.sub.6)-alkylcarbonyloxy which is unsubstituted or
substituted by R.sup.5, or is (C.sub.2-C.sub.6)-alkenylcarbonyloxy,
(C.sub.2-C.sub.6)-alkynylcarbonyloxy,
(C.sub.1-C.sub.8)-alkylsulfonyl, phenyl,
phenyl-(C.sub.1-C.sub.6)-alkoxy, phenyl-(C.sub.1-C.sub.6)-alkoxyc-
arbonyl, phenoxy, phenoxy-(C.sub.1-C.sub.6)-alkoxy,
phenoxy-(C.sub.1-C.sub.6)-alkoxycarbonyl, phenylcarbonyloxy,
phenylcarbonylamino, phenyl-(C.sub.1-C.sub.6)-alkylcarbonylamino,
for the phenyl ring being the last-mentioned 9 radicals
unsubstituted or mono- or polysubstituted, preferably up to
trisubstituted, by radicals R.sup.52; SiR'.sub.3, OSiR'.sub.3,
R'.sub.3Si--(C.sub.1-C.sub.8)-alkoxy, --CO--O--NR'.sub.2,
--O--N.dbd.CR'.sub.2, --N.dbd.CR'.sub.2, --O--NR'.sub.2,
--NR'.sub.2, --CH(OR').sub.2, --O--(CH.sub.2).sub.m--CH(O-
R').sub.2, --CR'"(OR').sub.2, --O--(CH.sub.2).sub.mCR'"(OR").sub.2
or by R"O--CHR'"CHCOR"--(C.sub.1-C.sub.6)-alkoxy, R.sup.51 is
identical or different and is halogen, nitro,
(C.sub.1-C.sub.4)-alkoxy and phenyl which is unsubstituted or
substituted by one or more, preferably up to three, radicals
R.sup.51; R.sup.52 is identical or different and is halogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-haloalkoxy or nitro;
R' is identical or different and is hydrogen,
(C.sub.1-C.sub.4)-alkyl, phenyl which is unsubstituted or
substituted by one or more, preferably up to three, radicals
R.sup.52, or two radicals R' together form a
(C.sub.2-C.sub.6)-alkanediyl chain; R" is identical or different
and is (C.sub.1-C.sub.4)-alkyl, or two radicals R" together form a
(C.sub.2-C.sub.6)-alkanediyl chain; R'" is hydrogen or
(C.sub.1-C.sub.4)-alkyl; m is 0, 1, 2, 3, 4, 5 or 6.
3. The herbicidal composition as claimed in claim 1, comprising
safeners of the formula (II) and/or (III) wherein the symbols and
indices have the following definitions: R.sup.24 is hydrogen,
(C.sub.1-C.sub.8)-alkyl or (C.sub.3-C.sub.7)-cycloalkyl, the above
carbon-containing radicals being unsubstituted or mono- or
polysubstituted by halogen or mono- or disubstituted, by preference
monosubstituted, by radicals R.sup.50, R.sup.50 is identical or
different and is hydroxyl, (C.sub.1-C.sub.4)-alkoxy, carboxyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.2-C.sub.6)-alkenyloxycarbonyl,
(C.sub.2-C.sub.6)-alkynyloxycarbony- l,
1-(hydroxyimino)-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkylimi- no]-(C.sub.1-C.sub.4)-alkyl and
1-[(C.sub.1-C.sub.4)-alkoxyimino]-(C.sub.1- -C.sub.4)-alkyl;
--SiR'.sub.3, --O--N.dbd.CR'.sub.2, --N.dbd.CR'.sub.2, --NR'.sub.2
and ONR'.sub.2 where R' is identical or different and is hydrogen,
(C.sub.1-C.sub.4)-alkyl or, as a pair, a
(C.sub.4-C.sub.5)-alkanediyl chain, R.sup.27, R.sup.28, R.sup.29
are identical or different and are hydrogen,
(C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.6)-haloalkyl,
(C.sub.3-C.sub.7)-cycloalkyl or phenyl which is unsubstituted or
substituted by one or more radicals selected from the group
consisting of halogen, cyano, nitro, amino, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkylthio and
(C.sub.1-C.sub.4)-alkylsulfonyl; R.sup.17, R.sup.19 are identical
or different and are hydrogen, halogen, methyl, ethyl, methoxy,
ethoxy, (C.sub.1 or C.sub.2)-haloalkyl, by preference hydrogen,
halogen or (C.sub.1 or C.sub.2)-haloalkyl.
4. The herbicidal composition as claimed in claim 1, comprising
safeners of the formula (II) wherein the symbols and indices have
the following definitions: R.sup.17 is halogen, nitro or
(C.sub.1-C.sub.4)-haloalkyl; n' is 1, 2 or 3; R.sup.18 is a radical
of the formula OR.sup.24; R.sup.24 is hydrogen,
(C.sub.1-C.sub.8)-alkyl or (C.sub.3-C.sub.7)-cycloalkyl, where the
above carbon-containing radicals are unsubstituted or mono- or
polysubstituted, by preference up to trisubstituted, by identical
or different halogen radicals or up to disubstituted, by preference
monosubstituted, by identical or different radicals selected from
the group consisting of hydroxyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.2-C.sub.6)-alkenyloxycarbonyl,
(C.sub.2-C.sub.6)-alkynyloxycarbonyl,
1-(hydroxyimino)-(C.sub.1-C.sub.4)-- alkyl,
1-[(C.sub.1-C.sub.4)-alkylimino]-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkoxyimino]-(C.sub.1-C.sub.4)-alkyl and
radicals of the formulae --SiR'.sub.3, --O--N.dbd.R'.sub.2,
--N.dbd.CR'.sub.2, --NR'.sub.2 and --O--NR'.sub.2, where the
radicals R' in the above-mentioned formulae are identical or
different and are hydrogen, (C.sub.1-C.sub.4)-alkyl or, as a pair,
are (C.sub.4 or C.sub.5)-alkanediyl; R.sup.27, R.sup.28, R.sup.29
are identical or different and are hydrogen,
(C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.6)-haloalkyl,
(C.sub.3-C.sub.7)-cycloalkyl or phenyl which is unsubstituted or
substituted by one or more of the radicals selected from the group
consisting of halogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy, nitro, (C.sub.1-C.sub.4)-haloalkyl and
(C.sub.1-C.sub.4)-haloalkoxy.
5. The herbicidal composition as claimed in claim 1, comprising
compounds of the formula (I) wherein the symbols and indices have
the following definitions: R.sup.1 is nitro, cyano, chlorine,
fluorine, methyl, trifluoromethyl, methylsulfonyl or ethylsulfonyl;
R.sup.2 is pentafluoroethoxymethyl, 2,2-difluoroethoxymethyl,
2,2,2-trifluoroethoxymethyl, 2,2,3,3-tetrafluoropropoxymethyl,
cyclopentyloxymethyl, cyclohexyloxymethyl, cyclopropyloxy,
tetrahydrofuran-2-ylmethoxymethyl, methoxyethoxyethoxymethyl, or
4,5-dihydroisoxazol-3-yl which is substituted by a radical from the
group consisting of cyanomethyl, ethoxymethyl and methoxymethyl;
R.sup.3 is OR.sup.5; R.sup.5 is hydrogen; a is 2; b is 0, and the
two radicals R.sup.1 are in positions 2 and 4 of the phenyl
ring.
6. The herbicidal composition as claimed in claim 1, wherein the
ratio of herbicide to safener is from 1:10 to 10:1.
7. The herbicidal composition as claimed in claim 1, comprising a
further herbicide.
8. A method of controlling weed plants in crops which comprises
applying a herbicidally active amount of a herbicidal composition
as claimed in claim 1 to the weed plants, plants, seeds of plants,
or the area on which the plants are growing.
9. The method as claimed in claim 8, wherein the plants are from
the group consisting of sugar cane, corn, wheat, rye, barley, oats,
rice, sorghum, cotton, and soya.
10. The method as claimed in claim 8, wherein the plants have been
genetically modified.
Description
[0001] The invention pertains to the technical field of crop
protectants, especially herbicide/antidote combinations (active
substance/safener combinations) suitable for use against competing
weed plants in crop plant cultures.
[0002] Numerous active herbicidal substances are known to be
inhibitors of the enzyme p-hydroxyphenylpyruvate dioxygenase
(HPPD). For instance, Proc. Br. Crop Prot. Conf. Weeds, 1991,1, 51;
Proc. Br. Crop Prot. Conf. Weeds, 1995,1, 35 disclose
benzoylcyclohexanediones, benzoylpyrazoles, and benzoylisoxazoles
of this kind. More recently, further such active substances have
been disclosed, for example, in WO 00/21924 and WO 01/07422.
[0003] As with many other active herbicidal substances, these HPPD
inhibitors too are not always sufficiently compatible with (i.e.,
lack sufficient selectivity for) certain important crop plants,
such as corn, rice or cereals, whereby imposing narrow limitations
on their use. In some crops, therefore, they cannot be used, or can
be used only at such low application rates that the desired broad
herbicidal activity toward weed plants is not ensured. More
particularly, many of these herbicides lack complete selectivity
for weed plants in corn, rice, cereals, sugar cane, and certain
other crops.
[0004] A known means for overcoming these disadvantages is to use
active herbicidal substances in combination with a substance known
as a safener or antidote. EP-A 0 943 240, WO 99/66795, and WO
00/30447, for example, describe various combinations of certain
HPPD inhibitors with safeners.
[0005] A safener is a compound which eliminates or lessens the
phytotoxic properties of a herbicide toward crop plants without
substantially reducing the herbicidal action toward weed
plants.
[0006] Identifying a safener for a particular group of herbicides
is still a difficult task, since the precise mechanisms by which a
safener lessens the noxious effect of herbicides are unknown.
Consequently, the fact that a compound acts as safener in
combination with one particular herbicide does not permit
conclusions as to the safener action of such a compound with other
groups of herbicides. In the use of safeners to protect crop plants
against herbicide damage, it has been found that the safeners in
many cases may still have certain disadvantages. These include the
following:
[0007] the safener lessens the action of the herbicides toward the
weed plants;
[0008] the crop plant protecting properties are inadequate;
[0009] with a given herbicide, the spectrum of crop plants in which
the safener/herbicide combination is to be used is too small;
[0010] a sufficiently large number of herbicides cannot be combined
with a given safener.
[0011] It is an object of the present invention to provide further
combinations of herbicides from the group of the HPPD inhibitors
with safeners that are suitable for raising the selectivity of
these herbicides with respect to important crop plants.
[0012] Novel combinations have now been found of certain herbicides
from the group of the HPPD inhibitors which carry selected
substituents in position 3 of the benzoyl moiety with numerous
other compounds which raise the selectivity of these herbicides
with respect to important crop plants.
[0013] The invention accordingly provides a herbicidally active
composition comprising
[0014] A) a herbicidally effective amount of one or more compounds
of the formula (I) 1
[0015] in which the symbols and indices have the following
definitions:
[0016] R.sup.1 is nitro, amino, halogen, cyano,
(C.sub.1-C.sub.4)-alkyl, (C.sub.2-C.sub.4)-alkenyl,
(C.sub.2-C.sub.4)-alkynyl, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.2-C.sub.4)-haloalkenyl, (C.sub.2-C.sub.4)-haloalkynyl,
(C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-haloalkylthio,
(C.sub.1-C.sub.4)-alkoxycarbonyl, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-alkylthio,
(C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkylcarbonyl,
(C.sub.1-C.sub.4)-alkylaminosulfonyl,
(C.sub.1-C.sub.4)-dialkylaminosulfonyl,
(C.sub.1-C.sub.4)-alkylcarbamoyl,
(C.sub.1-C.sub.4)-dialkylcarbamoyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.s- ub.4)-alkyl,
(C.sub.1-C.sub.4)-alkylamino or (C.sub.1-C.sub.4)-dialkylamin-
o;
[0017] R.sup.2 is
(C.sub.1-C.sub.4)-haloalkoxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)--
alkoxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.3-C.sub.6)-cycloalkoxy-(C.sub.1-C.- sub.4)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl-(C.sub.1-C.sub.4)-alkoxy,
tetrahydrofuran-2-yl-methoxy-(C.sub.1-C.sub.4)-alkyl,
tetrahydrofuran-3-yl-methoxy-(C.sub.1-C.sub.4)-alkyl or a
heterocyclic radical from the group consisting of isoxazol-3-yl and
4,5-dihydroisoxazol-3-yl which is substituted by a radical from the
group consisting of cyanomethyl, ethoxymethyl and
methoxymethyl;
[0018] R.sup.3 is OR.sup.5, cyano, halogen, cyanato, thiocyanato,
(C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkylsulfinyl,
(C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.2-C.sub.4)-alkenylthio,
(C.sub.2-C.sub.4)-alkenylsulfinyl,
(C.sub.2-C.sub.4)-alkenylsulfonyl, (C.sub.2-C.sub.4)-alkynylthio,
(C.sub.2-C.sub.4)-alkynylsulfinyl,
(C.sub.2-C.sub.4)-alkynylsulfonyl, (C.sub.1-C.sub.4)-haloalkylthio,
(C.sub.2-C.sub.4)-haloalkenylthio,
(C.sub.2-C.sub.4)-haloalkynylthio,
(C.sub.1-C.sub.4)-haloalkylsulfinyl,
(C.sub.2-C.sub.4)-haloalkenylsulfiny- l,
(C.sub.2-C.sub.4)-haloalkynylsulfinyl,
(C.sub.1-C.sub.4)-haloalkylsulfo- nyl,
(C.sub.2-C.sub.4)-haloalkenylsulfonyl or
(C.sub.2-C.sub.4)-haloalkyny- lsulfonyl;
[0019] R.sup.4 is (C.sub.1-C.sub.4)-alkyl;
[0020] R.sup.5 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl or
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)- -alkyl;
[0021] a is 0, 1, 2 or 3;
[0022] b is 0, 1 or 2;
[0023] and
[0024] B) an antidote-active amount of one or more compounds from
groups a) to e): a) compounds of the formulae (II) to (IV), 2
[0025] in which the symbols and indices have the following
definitions:
[0026] n' is a natural number from 0 to 5, preferably from 0 to
3;
[0027] T is a (C.sub.1- or C.sub.2-)-alkanediyl chain which is
unsubstituted or substituted by one or two (C.sub.1-C.sub.4)-alkyl
radicals or by [(C.sub.1-C.sub.3)-alkoxy]carbonyl;
[0028] W is a radical from the group (W1) to (W4), 3
[0029] m' is 0 or 1;
[0030] R.sup.17 and R.sup.19 are identical or different and are
halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, nitro
or (C.sub.1-C.sub.4)-haloalkyl;
[0031] R.sup.18 and R.sup.20 are identical or different and are
OR.sup.24, SR.sup.24 or NR.sup.24R.sup.25 or a saturated or
unsaturated 3- to 7-membered heterocycle containing at least one
nitrogen atom and up to 3 heteroatoms which is bonded by the
nitrogen atom to the carbonyl group in (II) or (III) and is
unsubstituted or substituted by radicals from the group consisting
of (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy and
unsubstituted or substituted phenyl, preferably a radical of the
formula OR.sup.24, NHR.sup.25 or N(CH.sub.3).sub.2, in particular
of the formula OR.sup.24;
[0032] R.sup.24 is hydrogen or an unsubstituted or substituted
aliphatic hydrocarbon radical, preferably having a total of from 1
to 18 carbon atoms;
[0033] R.sup.25 is hydrogen, (C.sub.1-C.sub.6)-alkyl,
(C.sub.1-C.sub.6)-alkoxy or substituted or unsubstituted
phenyl;
[0034] R.sup.26 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.8)-haloalkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-a- lkyl,
(C.sub.1-C.sub.6)-hydroxyalkyl, (C.sub.3-C.sub.12)-cycloalkyl or
tri-(C.sub.1-C.sub.4)-alkylsilyl;
[0035] R.sup.27, R.sup.28 and R.sup.29 are identical or different
and are hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.6)-haloalkyl, (C.sub.3-C.sub.12)-cycloalkyl or
substituted or unsubstituted phenyl;
[0036] R.sup.21 is (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.2-C.sub.4)-alkenyl,
(C.sub.2-C.sub.4)-haloalkenyl, (C.sub.3-C.sub.7)-cycloalkyl,
preferably dichloromethyl;
[0037] R.sup.22, R.sup.23 are identical or different and are
hydrogen, (C.sub.0-C.sub.4)-alkyl, (C.sub.2-C.sub.4)-alkenyl,
(C.sub.2-C.sub.4)-alkynyl, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.2-C.sub.4)-haloalkenyl,
(C.sub.1-C.sub.4)-alkylcarbamoyl-(C.sub.1-- C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenylcarbamoyl-(C.sub.1-C.sub.4)-alkyl- ,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl,
dioxolanyl-(C.sub.1-C.sub.4)-alkyl, thiazolyl, furyl, furylalkyl,
thienyl, piperidyl, substituted or unsubstituted phenyl, or
R.sup.22 and R.sup.23 together form a substituted or unsubstituted
heterocyclic ring, preferably an oxazolidine, thiazolidine,
piperidine, morpholine, hexahydropyrimidine or benzoxazine
ring;
[0038] b) one or more compounds from the following group:
[0039] 1,8-naphthalic anhydride,
[0040] methyl diphenylmethoxyacetate,
[0041] cyanomethoxyimino(phenyl)acetonitrile (cyometrinile),
[0042] 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile
(oxabetrinil),
[0043] 4'-chloro-2,2,2-trifluoroacetophenone
O-1,3-dioxolan-2-ylmethyl oxime (fluxofenim),
[0044] 4,6-dichloro-2-phenylpyrimidine (fenclorim),
[0045] benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate
(flurazole),
[0046] 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),
[0047] N-(4-methylphenyl)-N'-(1-methyl-1-phenylethyl)urea
(dymron),
[0048] 1-[4-(N-2-methoxybenzoylsulfarnoyl)phenyl]-3-methylurea,
[0049]
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
[0050]
1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
[0051] 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,
[0052] (2,4-dichlorophenoxy)acetic acid (2,4-D),
[0053] (4-chlorophenoxy)acetic acid,
[0054] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
[0055] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
[0056] (4-chloro-o-tolyloxy)acetic acid (MCPA),
[0057] 4-(4-chloro-o-tolyloxy)butyric acid,
[0058] 4-(4-chlorophenoxy)butyric acid,
[0059] 3,6-dichloro-2-methoxybenzoic acid (dicamba),
[0060] 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate
(lactidichlor)
[0061] and their salts and esters, preferably
(C.sub.1-C.sub.8);
[0062] c) N-acylsulfonamides of the formula (V) and their salts,
4
[0063] in which
[0064] R.sup.30 is hydrogen, a carbon-containing radical such as a
hydrocarbon radical, a hydrocarbon-oxy radical, a hydrocarbon-amino
radical, a hydrocarbon-thio radical or a heterocyclyl radical, each
of the 4 last-mentioned radicals being unsubstituted or being
substituted by one or more identical or different radicals selected
from the group consisting of halogen, cyano, nitro, amino,
hydroxyl, carboxyl, formyl, carboxamide, sulfonamide and radicals
of the formula --Z.sup.a--R.sup.a, each hydrocarbon moiety
preferably having 1 to 20 carbon atoms and a carbon-containing
radical R.sup.+ inclusive of substituents preferably having 1 to 30
carbon atoms;
[0065] R.sup.31 is hydrogen or (C.sub.1-C.sub.4)-alkyl, preferably
hydrogen, or
[0066] R.sup.30 and R.sup.31 together with the group of the formula
--CO--N-- are the residue of a 3- to 8-membered saturated or
unsaturated ring;
[0067] R.sup.32 is identical or different and is halogen, cyano,
nitro, amino, hydroxyl, carboxyl, formyl, CONH.sub.2,
SO.sub.2NH.sub.2 or a radical of the formula --Z--R.sup.b;
[0068] R.sup.33 s hydrogen or (C.sub.1-C.sub.4)-alkyl, preferably
hydrogen;
[0069] R.sup.34 is identical or different and is halogen, cyano,
nitro, amino, hydroxyl, carboxyl, CHO, CONH.sub.2, SO.sub.2NH.sub.2
or a radical of the formula --Z.sup.c--R.sup.c;
[0070] R.sup.a is a hydrocarbon radical or a heterocyclyl radical,
each of the two last-mentioned radicals being unsubstituted or
substituted by one or more identical or different radicals selected
from the group consisting of halogen, cyano, nitro, amino,
hydroxyl, mono- and di-[(C.sub.1-C.sub.4)-alkyl]amino, or an alkyl
radical in which a plurality, preferably 2 or 3, non-adjacent
CH.sub.2 groups are in each case replaced by one oxygen atom;
[0071] R.sup.b,R.sup.c are identical or different and are a
hydrocarbon radical or a heterocyclyl radical, each of the two
last-mentioned radicals being unsubstituted or substituted by one
or more identical or different radicals selected from the group
consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl,
halo-(C.sub.1-C.sub.4)-alkoxy, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino, or an alkyl radical in which a
plurality, preferably 2 or 3, non-adjacent CH.sub.2 groups are
replaced in each case by one oxygen atom;
[0072] Z.sup.a is a divalent group of the formula --O--, --S--,
--CO--, --CS--, --CO--O--, --CO--S--, --O--CO--, --S--CO--, --SO--,
--SO.sub.2--, --NR*--, --CO--NR*--, --NR*--CO--, --SO.sub.2--NR*--
or --NR*--SO.sub.2--, the bond given on the right-hand side of each
of the divalent groups being the bond to the radical R.sup.a, and
the radicals R* in the 5 last-mentioned radicals independently of
each other being in each case H, (C.sub.1-C.sub.4)-alkyl or
halo-(C.sub.1-C.sub.4)-alkyl;
[0073] Z.sup.b,Z.sup.c independently of one another are a direct
bond or a divalent group of the formula --O--, --S--, --CO--,
--CS--, --CO--O--, --CO--S--, --O--CO--, --S--CO--, --SO,
SO.sub.2--, --NR*--, --SO.sub.2--NR*--, --NR*--SO.sub.2--,
--CO--NR*-- or --NR*--CO--, the bond given on the right-hand side
of each of the divalent groups being the bond is linked to the
radical R.sup.b or R.sup.c and the radicals R* in the 5
last-mentioned radicals independently of one another are in each
case H, (C.sub.1-C.sub.4)-alkyl or
halo-(C.sub.1-C.sub.4)-alkyl;
[0074] n is an integer from 0 to 4, preferably 0, 1 or 2, in
particular 0 or 1, and
[0075] m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in
particular 0, 1 or 2;
[0076] d) acylsulfamoylbenzamides of the formula (VI), optionally
also in salt form, 5
[0077] in which
[0078] X.sup.3 is CH or N;
[0079] R.sup.35 is hydrogen, heterocyclyl or a hydrocarbon radical,
the two last-mentioned radicals optionally being substituted by one
or more identical or different radicals selected from the group
consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl,
CHO, CONH.sub.2, SO.sub.2NH.sub.2 and Z.sup.a--R.sup.a;
[0080] R.sup.36 is hydrogen, hydroxyl, (C.sub.1-C.sub.6)-alkyl,
(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl,
(C.sub.1-C.sub.6)-alkoxy, (C.sub.2-C.sub.6)-alkenyloxy, the five
last-mentioned radicals optionally being substituted by one or more
identical or different radicals selected from the group consisting
of halogen, hydroxyl, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy and (C.sub.1-C.sub.4)-alkylthio, or
[0081] R.sup.35 and R.sup.36together with the nitrogen atom to
which they are attached are a 3- to 8-membered saturated or
unsaturated ring;
[0082] R.sup.37 is halogen, cyano, nitro, amino, hydroxyl,
carboxyl, CHO, CONH.sub.2, SO.sub.2NH.sub.2 or
Z.sup.b--R.sup.b;
[0083] R.sup.38 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.2-C.sub.4)-alkenyl or (C.sub.2-C.sub.4)-alkynyl;
[0084] R.sup.39 is halogen, cyano, nitro, amino, hydroxyl,
carboxyl, phosphoryl, CHO, CONH.sub.2, SO.sub.2NH.sub.2 or
Z.sup.c--R.sup.c;
[0085] R.sup.a is a (C.sub.2-C.sub.20)-alkyl radical whose carbon
chain is interrupted once or more than once by oxygen atoms, or is
heterocyclyl or a hydrocarbon radical, the two last-mentioned
radicals optionally being substituted by one or more identical or
different radicals selected from the group consisting of halogen,
cyano, nitro, amino, hydroxyl, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino;
[0086] R.sup.b, R.sup.c are identical or different and are a
(C.sub.2-C.sub.20)-alkyl radical whose carbon chain is interrupted
once or more than once by oxygen atoms, or a heterocyclyl or a
hydrocarbon radical, the two last-mentioned radicals optionally
being substituted by one or more identical or different radicals
selected from the group consisting of halogen, cyano, nitro, amino,
hydroxyl, phosphoryl, (C.sub.1-C.sub.4)-haloalkoxy, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino- ;
[0087] Z.sup.a is a divalent unit selected from the group
consisting of O, S, CO, CS, C(O)O, C(O)S, SO, SO.sub.2, NR.sup.d,
C(O)NR.sup.d or SO.sub.2NR.sup.d;
[0088] Z.sup.b, Z.sup.c are identical or different and are a direct
bond or a divalent unit selected from the group consisting of O, S,
CO, CS, C(O)O, C(O)S, SO, SO.sub.2, NR.sup.d, SO.sub.2NR.sup.d or
C(O)NR.sup.d;
[0089] R.sup.d is hydrogen, (C.sub.1-C.sub.4)-alkyl or
(C.sub.1-C.sub.4)-haloalkyl;
[0090] r is an integer from 0 to 4, and
[0091] q in the event that X.sup.3 is CH, is an integer from 0 to 5
and, in the event that X is N, is an integer from 0 to 4;
[0092] e) compounds of the formula (VII), 6
[0093] in which the symbols and indices have the following
definitions:
[0094] X is CH or N,
[0095] p in the event that X=N, is an integer from 0 to 2 and, in
the event that X=CH, is an integer from 0 to 3;
[0096] R.sup.40 is halogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkoxy, nitro, (C.sub.1-C.sub.4)-alkylthio,
(C.sub.1-C.sub.4)-alkylsulfonyl, (C.sub.1-C.sub.4)-alkoxycarbonyl,
phenyl or phenoxy, the two last-mentioned radicals being
unsubstituted or substituted by one or more, preferably up to
three, identical or different radicals from the group consisting of
halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.1-C.sub.4)-alkoxy, halo-(C.sub.1-C.sub.4)-alkoxy, nitro and
cyano;
[0097] R.sup.41 is hydrogen or (C.sub.1-C.sub.4)-alkyl, and
[0098] R.sup.42 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl,
(C.sub.2-C.sub.6)-alkynyl or aryl, each of the aforementioned
carbon-containing radicals being unsubstituted or substituted by
one or more, preferably up to three, identical or different
radicals from the group consisting of halogen, nitro, cyano,
hydroxyl, (C.sub.1-C.sub.8)-alkoxy, in which one or more,
preferably up to three, CH.sub.2 groups may be replaced by oxygen,
(C.sub.1-C.sub.4)-alkylthio, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.4)-alkenyloxy and
(C.sub.2-C.sub.4)-alkynyloxy,
[0099] inclusive of the stereoisomers and the agriculturally
customary salts.
[0100] A herbicidally effective amount is, for the purposes of the
invention, an amount of one or more herbicides which is capable of
adversely affecting plant growth.
[0101] An antidote-active amount is, for the purposes of the
invention, an amount of one or more safeners which is capable of at
least partially countering the phytotoxic effect of a herbicide or
herbicide mixture on a crop plant.
[0102] Unless otherwise defined individually, the following
definitions generally apply to the radicals in the formulae (I) to
(VIII) and subsequent formulae.
[0103] The radicals alkyl, alkoxy, haloalkyl, haloalkoxy,
alkylamino and alkylthio and the corresponding unsaturated and/or
substituted radicals can be in each case straight-chain or branched
in the carbon skeleton. Alkyl radicals, also the composite meanings
such as alkoxy, haloalkyl and the like, preferably have 1 to 4
carbon atoms and are, for example, methyl, ethyl, n- or i-propyl or
n-, i-, t- or 2-butyl. Alkenyl and alkynyl radicals have the
meanings of the unsaturated radicals which are possible and which
correspond to the alkyl radicals; alkenyl is, for example, allyl,
1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl,
but-3-en-1-yl, 1-methylbut-3-en-1-yl and I-methylbut-2-en-1-yl.
Alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl,
1-methylbut-3-yn-1-yl. "(C.sub.1-C.sub.4)-Alkyl" is the
abbreviation for alkyl having 1 to 4 carbon atoms; the same applies
analogously to other general definitions of radicals, where the
ranges of the possible number of carbon atoms are indicated in
brackets.
[0104] Cycloalkyl is, preferably, a cyclic alkyl radical having 3
to 8, preferably 3 to 7, especially preferably 3 to 6, carbon
atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and
cyclohexyl. Cycloalkenyl and cycloalkynyl denote corresponding
unsaturated compounds.
[0105] Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl,
haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl which are
partially or fully substituted by halogen, preferably by fluorine,
chlorine and/or bromine, in particular by fluorine or chlorine, for
example CF.sub.3, CHF.sub.2, CH.sub.2F, CF.sub.2CF.sub.3,
CH.sub.2FCCIFM, CCl.sub.3, CHCl.sub.2, CH.sub.2CH.sub.2Cl.
Haloalkoxy is, for example, OCF.sub.3, OCHF.sub.2, OCH.sub.2F,
OCF.sub.2CF.sub.3, OCH.sub.2CF.sub.3 and OCH.sub.2CH.sub.2Cl. This
also applies analogously to other halogen-substituted radicals.
[0106] An aliphatic hydrocarbon radical is generally a
straight-chain or branched saturated or unsaturated hydrocarbon
radical, preferably having 1 to 18, especially preferably 1 to 12,
carbon atoms, for example alkyl, alkenyl or alkynyl. Aryl is
generally a mono-, bi- or polycyclic aromatic system having
preferably 6 to 14 carbon atoms, for example phenyl, naphthyl,
pentalenyltetrahydronaphthyl, indenyl, indanyl and fluorenyl,
especially preferably phenyl. Aliphatic hydrocarbon radical
preferably means alkyl, alkenyl or alkynyl having up to 12 carbon
atoms; the same applies analogously to an aliphatic hydrocarbon
radical in a hydrocarbon-oxy radical.
[0107] Heterocyclic ring, heterocyclic radical or heterocyclyl is a
mono-, bi- or polycyclic ring system which is saturated,
unsaturated and/or aromatic and contains one or more, preferably 1
to 4, heteroatoms, preferably selected from the group consisting of
N, S and O. Preferred are saturated heterocycles having 3 to 7 ring
atoms and one or two heteroatoms selected from the group consisting
of N, O and S, chalcogens not being adjacent. Especially preferred
are monocyclic rings having 3 to 7 ring atoms and a heteroatom
selected from the group consisting of N, O and S, and also
morpholine, dioxolane, piperazine, imidazoline and oxazolidine.
Very especially preferred saturated heterocycles are oxirane,
pyrrolidone, morpholine and tetrahydrofuran. Also preferred are
partially unsaturated heterocycles having 5 to 7 ring atoms and one
or two heteroatoms selected from the group consisting of N, O and
S. Especially preferred are partially unsaturated heterocycles
having 5 to 6 ring atoms and one heteroatom selected from the group
consisting of N, O and S. Very especially preferred partially
unsaturated heterocycles are pyrazoline, imidazoline and
isoxazoline. Equally preferred are mono- or bicyclic aromatic
heterocycles having 5 to 6 ring atoms which contain one to four
heteroatoms selected from the group consisting of N, O, S,
chalcogens not being adjacent. Especially preferred are monocyclic
aromatic heterocycles having 5 to 6 ring atoms which contain a
heteroatom selected from the group consisting of N, O and S, and
also pyrimidine, pyrazine, pyridazine, oxazole, thiazole,
thiadiazole, oxadiazole, pyrazole, triazole and isoxazole. Very
especially preferred are pyrazole, thiazole, triazole and
furan.
[0108] Substituted radicals, such as substituted hydrocarbon
radicals, for example substituted alkyl, alkenyl, alkynyl, aryl,
phenyl and arylalkyl such as benzyl, or substituted heterocyclyl or
heteroaryl, are a substituted radical which is derived from the
unsubstituted parent structure, the substituents being, by
preference, one or more, preferably 1, 2 or 3, in the case of Cl
and F also up to the maximum possible number of, radicals selected
from the group consisting of halogen, alkoxy, haloalkoxy,
alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido,
alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and
dialkylaminocarbonyl, substituted amino such as acylamino, mono-
and dialkylamino and alkylsulfinyl, haloalkylsulfinyl,
alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic
radicals, also alkyl and haloalkyl and the unsaturated aliphatic
radicals which correspond to the abovementioned saturated
hydrocarbon-containing substituents, preferably alkenyl, alkynyl,
alkenyloxy and alkynyloxy. In the case of radicals having carbon
atoms, those having 1 to 4 carbon atoms, in particular 1 or 2
carbon atoms, are preferred. As a rule, preferred radicals are
those selected from the group consisting of halogen, for example
fluorine or chlorine, (C.sub.1-C.sub.4)-alkyl, preferably methyl or
ethyl, (C.sub.1-C.sub.4)-haloalkyl, preferably trifluoromethyl,
(C.sub.1-C.sub.4)-alkoxy, preferably methoxy or ethoxy,
(C.sub.1-C.sub.4)-haloalkoxy, nitro and cyano. Especially preferred
in this context are the substituents methyl, methoxy and
chlorine.
[0109] Mono- or disubstituted amino is a chemically stable radical
selected from the group of the substituted amino radicals which are
N-substituted by, for example, one or two identical or different
radicals selected from the group consisting of alkyl, alkoxy, acyl
and aryl; preferably monoalkylamino, dialkylamino, acylamino,
arylamino, N-alkyl-N-arylamino and N-heterocycles. Preferred in
this context are alkyl radicals having 1 to 4 carbon atoms. By
preference, aryl is phenyl or substituted phenyl. By preference,
substituted aryl is substituted phenyl. The definition given
further below applies to acyl, preferably
(C.sub.1-C.sub.4)-alkanoyl. This also applies analogously to
substituted hydroxylamino or hydrazino.
[0110] By preference, optionally substituted phenyl is phenyl which
is unsubstituted or mono- or polysubstituted, preferably up to
trisubstituted, in the case of halogen such as Cl and F also up to
pentasubstituted, by identical or different radicals selected from
the group consisting of halogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.1-C.sub.4)-haloalkoxy and nitro, for example o-, m- and
p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and
4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and
2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
[0111] An acyl radical is the radical of an organic acid having by
preference up to 6 carbon atoms, for example the radical of a
carboxylic acid and radicals of acids derived therefrom, such as
thiocarboxylic acid, optionally N-substituted iminocarboxylic
acids, or the radical of carbonic monoesters, optionally
N-substituted carbamic acids, sulfonic acids, sulfinic acids,
phosphonic acids, phosphinic acids. Acyl is, for example, formyl,
alkylcarbonyl such as (C.sub.1-C.sub.4-alkyl)carbonyl,
phenylcarbonyl, it being possible for the phenyl ring to be
substituted, for example as indicated above for phenyl, or
alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl,
alkylsulfonyl, alkylsulfinyl or N-alkyl-1-iminoalkyl.
[0112] All stereoisomers which show the same topological linkage of
the atoms, and their mixtures, also fall under the formulae (I) to
(VIII). Such compounds contain one or more asymmetric carbon atoms
or else double bonds which are not indicated specifically in the
general formulae. The stereoisomers which are possible which are
defined by their specific spatial form, such as enantiomers,
diastereomers, Z- and E-isomers, can be obtained from mixtures of
the stereoisomers by customary methods or else be prepared by
stereoselective reactions in combination with the use of
stereochemically pure starting materials.
[0113] Herbicidally active substances which are suitable in
accordance with the invention are those compounds of the formula
(I) which, on their own, cannot be used, or not optimally used, in
crops of useful plants such as cereal crops, rice or corn because
they are too harmful to the crop plants.
[0114] Herbicides of the formula (I) are known, for example, from
WO-A 00/21924 and WO-A 01/7422.
[0115] The cited publications contain extensive data on preparation
processes and starting materials. These publications are referred
to exclusively and are considered by such reference to be part of
this description.
[0116] The compounds of the formula (II) are known, for example,
from EP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (U.S. Pat. No.
4,891,057), EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0
346 620 (WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA
94/7120) and the literature cited therein or can be prepared by or
analogously to the processes described therein. The compounds of
the formula (III) are known from EP-A-0 086 750, EP-A-0 94349 (U.S.
Pat. No. 4,902,340), EP-A-0 191736 (U.S. Pat. No. 4,881,966) and
EP-A-0 492 366 and the literature cited therein or can be prepared
by or analogously to the processes described therein. Furthermore,
some compounds are described in EP-A-0 582 198. The compounds of
the formula (II) are known from a large number of patent
applications, for example U.S. Pat. No. 4,021,224 and U.S. Pat. No.
4,021,229. Moreover, compounds of group (b) are known from
CN-A-87/102 789, EP-A-0 365 484 and from "The Pesticide Manual",
The British Crop Protection Council and the Royal Society of
Chemistry, 11th edition, Farnham 1997. The compounds of group (c)
are described in WO-A-97/45016, those of group (d) in German Patent
Application 197 42 951.3 and those of group (e) in WO-A 98/13
361.
[0117] The publications cited contain detailed information on
preparation processes and starting materials. These publications
are referred to explicitly and are considered by such reference to
be part of this description.
[0118] For the purpose of the present specification, the terms
"herbicidal compositions" and "herbicide/safener combinations" are
to be understood as being synonymous.
[0119] Preference is given to herbicidal compositions comprising
compounds of the formula (I) wherein the symbols and indices have
the following definitions:
[0120] R.sup.1 is nitro, cyano, chlorine, fluorine, methyl,
trifluoromethyl, methylsulfonyl or ethylsulfonyl;
[0121] R.sup.2 is pentafluoroethoxymethyl,
2,2-difluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl,
2,2,3,3-tetrafluoropropoxymethyl, cyclopentyloxymethyl,
cyclohexyloxymethyl, cyclopropyloxy,
tetrahydrofuran-2-ylmethoxymethyl, methoxyethoxyethoxymethyl, or
4,5-dihydroisoxazol-3-yl substituted by a radical from the group
consisting of cyanomethyl, ethoxymethyl and methoxymethyl;
[0122] R.sup.3 is OR.sup.5;
[0123] R.sup.5 is hydrogen;
[0124] a is 2;
[0125] b is 0, and in which the two radicals R.sup.1 are in
positions 2 and 4 of the phenyl ring.
[0126] Preferred herbicidal compositions are those which comprise
safeners of the formula (II) and/or (III) wherein the symbols and
indices have the following definitions:
[0127] R.sup.24 is hydrogen, (C.sub.1-C.sub.18)-alkyl,
(C.sub.3-C.sub.12)-cycloalkyl, (C.sub.2-C.sub.8)-alkenyl and
(C.sub.2-C.sub.18)-alkynyl, where the carbon-containing groups can
be substituted by one or more, preferably up to three, radicals
R.sup.50;
[0128] R.sup.50 is identical or different and is halogen, hydroxyl,
(C.sub.1-C.sub.8)-alkoxy, (C.sub.1-C.sub.8)-alkylthio,
(C.sub.2-C.sub.8)-alkenylthio, (C.sub.2-C.sub.8)-alkynylthio,
(C.sub.2-C.sub.8)-alkenyloxy, (C.sub.2-C.sub.8)-alkynyloxy,
(C.sub.3-C.sub.7)-cycloalkyl, (C.sub.3-C.sub.7)-cycloalkoxy, cyano,
mono- and di-(C.sub.1-C.sub.4)-alkylamino, carboxyl,
(C.sub.1-C.sub.8)-alkoxyca- rbonyl,
(C.sub.2-C.sub.8)-alkenyloxycarbonyl, (C.sub.1-C.sub.8)-alkylthioc-
arbonyl, (C.sub.2-C.sub.8)-alkynyloxycarbonyl,
(C.sub.1-C.sub.8)-alkylcarb- onyl,
(C.sub.2-C.sub.8)-alkenylcarbonyl,
(C.sub.2-C.sub.8)-alkynylcarbonyl- ,
1-(hydroxyimino)-(C.sub.1-C.sub.6)-alkyl,
1-[(C.sub.1-C.sub.4)-alkylimin- o]-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkoxyimino]-(C.sub.1-C.s- ub.6)-alkyl,
(C.sub.1-C.sub.8)-alkylcarbonylamino, (C.sub.2-C.sub.8)-alken-
ylcarbonylamino, (C.sub.2-C.sub.8)-alkynylcarbonylamino,
aminocarbonyl, (C.sub.1-C.sub.8)-alkylaminocarbonyl,
di-(C.sub.1-C.sub.6)-alkylaminocarb- onyl,
(C.sub.2-C.sub.6)-alkenylaminocarbonyl,
(C.sub.2-C.sub.6)-alkynylami- nocarbonyl,
(C.sub.1-C.sub.8)-alkoxycarbonylamino, (C.sub.1-C.sub.8)-alkyl-
aminocarbonylamino, (C.sub.1-C.sub.6)-alkylcarbonyloxy which is
unsubstituted or substituted by R.sup.51, or is
(C.sub.2-C.sub.6)-alkenyl- carbonyloxy,
(C.sub.2-C.sub.6)-alkynylcarbonyloxy, (C.sub.1-C.sub.8)-alkyl-
sulfonyl, phenyl, phenyl-(C.sub.1-C.sub.6)-alkoxy,
phenyl-(C.sub.1-C.sub.6- )-alkoxycarbonyl, phenoxy,
phenoxy-(C.sub.1-C.sub.6)-alkoxy,
phenoxy-(C.sub.1-C.sub.6)-alkoxycarbonyl, phenylcarbonyloxy,
phenylcarbonylamino, phenyl-(C.sub.1-C.sub.6)-alkylcarbonylamino,
the last-mentioned 9 radicals on the phenyl ring being
unsubstituted or mono- or polysubstituted, preferably up to
trisubstituted, by radicals R.sup.52; SiR'.sub.3, --OSiR'.sub.3,
R'.sub.3Si-(C.sub.1-C.sub.8)-alkoxy, --CO--O--NR'.sub.2,
--O--N.dbd.CR.sub.12, --N.dbd.CR'.sub.2, --O--N--R'.sub.2,
--NR'.sub.2, CH(OR').sub.2, O--(CH.sub.2).sub.m-CH(OR')- .sub.2,
--CR'"(OR').sub.2, --O--(CH.sub.2).sub.mCR'"(OR").sub.2 or by
R"O--CHR'"CHCOR"--(C.sub.1-C.sub.6)-alkoxy,
[0129] R.sup.51 is identical or different and is halogen, nitro,
(C.sub.1-C.sub.4)-alkoxy and phenyl which is unsubstituted or
substituted by one or more, preferably up to three, radicals
R.sup.51;
[0130] R.sup.52 is identical or different and is halogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-haloalkoxy or
nitro;
[0131] R' is identical or different and is hydrogen,
(C.sub.1-C.sub.4)-alkyl, phenyl which is unsubstituted or
substituted by one or more, preferably up to three, radicals
R.sup.52, or two radicals R' together form a
(C.sub.2-C.sub.6)-alkanediyl chain;
[0132] R" is identical or different and is (C.sub.1-C.sub.4)-alkyl,
or two radicals R" together form a (C.sub.2-C.sub.6)-alkanediyl
chain;
[0133] R'" is hydrogen or (C.sub.1-C.sub.4)-alkyl;
[0134] w is 0, 1,2,3,4, 5 or 6.
[0135] Especially preferred are herbicidal compositions which
comprise safeners of the formula (II) and/or (III) wherein the
symbols and indices have the following definitions:
[0136] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl or
(C.sub.3-C.sub.7)-cycloalkyl, the above carbon-containing radicals
being unsubstituted or mono- or polysubstituted by halogen or mono-
or disubstituted, by preference monosubstituted, by radicals
R.sup.50,
[0137] R.sup.50 is identical or different and is hydroxyl,
(C.sub.1-C.sub.4)-alkoxy, carboxyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.2-C.sub.6)-alkenyloxycarbonyl,
(C.sub.2-C.sub.6)-alkynyloxycarbony- l,
1-(hydroxyimino)-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkylimi- no]-(C.sub.1-C.sub.4)-alkyl and
1-[(C.sub.1-C4)-alkoxyimino]-(C.sub.1-C.su- b.4)-alkyl;
--SiR'.sub.3, --O--N.dbd.CR'.sub.2, --N.dbd.CR'.sub.2, --NR'.sub.2
and --ONR'.sub.2 where R' is identical or different and is
hydrogen, (C.sub.1-C.sub.4)-alkyl or, as a pair, a
(C.sub.4-C.sub.5)-alkanediyl chain,
[0138] R.sup.27, R.sup.28, R.sup.29 are identical or different and
are hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.6)-haloalkyl,
(C.sub.3-C.sub.7)-cycloalkyl or phenyl which is unsubstituted or
substituted by one or more radicals selected from the group
consisting of halogen, cyano, nitro, amino, mono- and
di-[(C.sub.1-C.sub.4)-alkyl]amino- , (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-haloalkoxy, (C.sub.1-C.sub.4)-alkylthio and
(C.sub.1-C.sub.4)-- alkylsulfonyl;
[0139] R.sup.17, R.sup.19 are identical or different and are
hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, (C.sub.1 or
C.sub.2)-haloalkyl, by preference hydrogen, halogen or (C.sub.1 or
C.sub.2)-haloalkyl.
[0140] Especially preferred are herbicidal compositions comprising
safeners of the formula (II) in which the symbols and indices have
the following definitions:
[0141] R.sup.17 is hydrogen, halogen, nitro or
(C.sub.1-C.sub.4)-haloalkyl- ;
[0142] n' is 1, 2 or 3;
[0143] R.sup.18 is a radical of the formula OR.sup.24;
[0144] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl or
(C.sub.3-C.sub.7)-cycloalkyl, where the above carbon-containing
radicals are unsubstituted or mono- or polysubstituted, by
preference up to trisubstituted, by identical or different halogen
radicals or up to disubstituted, by preference monosubstituted, by
identical or different radicals selected from the group consisting
of hydroxyl, (C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.2-C.sub.6)-alkenyloxycarbonyl,
(C.sub.2-C.sub.6)-alkynyloxycarbony- l,
1-(hydroxyimino)-(C.sub.1-C.sub.4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkylimi- no]-(C.sub.--C4)-alkyl,
1-[(C.sub.1-C.sub.4)-alkoxyimino]-(C.sub.1-C.sub.4- )-alkyl and
radicals of the formulae --SiR'.sub.3, --O--N.dbd.R'.sub.2,
--N.dbd.CR'.sub.2, --NR'.sub.2 and --O--NR'.sub.2, where the
radicals R' in the above-mentioned formulae are identical or
different and are hydrogen, (C.sub.1-C.sub.4)-alkyl or, as a pair,
are (C.sub.4 or C.sub.5)-alkanediyl;
[0145] R.sup.27, R.sup.28, R.sup.29 are identical or different and
are hydrogen, (C.sub.1-C.sub.8)-alkyl, (C.sub.1-C.sub.6)-haloalkyl,
(C.sub.3-C.sub.7)-cycloalkyl or phenyl which is unsubstituted or
substituted by one or more of the radicals selected from the group
consisting of halogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy, nitro, (C.sub.1-C.sub.4)-haloalkyl and
(C.sub.1-C.sub.4)-haloalkoxy.
[0146] Also especially preferred are herbicidal compositions
comprising safeners of the formula (III) wherein the symbols and
indices have the following definitions:
[0147] R.sup.19 is hydrogen, halogen or
(C.sub.1-C.sub.4)-haloalkyl;
[0148] n' is 1, 2 or 3, where (R.sup.19).sub.n' is by preference
5-Cl;
[0149] R.sup.20 is a radical of the formula OR.sup.24;
[0150] T is CH.sub.2and
[0151] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.8)-haloalkyl or
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)- -alkyl, by preference
(C.sub.1-C.sub.8)-alkyl.
[0152] Especially preferred are herbicidal compositions comprising
safeners of the formula (II) wherein the symbols and indices have
the following definitions:
[0153] W is (W1);
[0154] R.sup.17 is hydrogen, halogen or
(C.sub.1-C.sub.2)-haloalkyl;
[0155] n' is 1, 2 or 3, where (R.sup.17).sub.n is by preference
2,4-Cl.sub.2;
[0156] R.sup.18 is a radical of the formula OR.sup.24;
[0157] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-hydroxyalkyl,
(C.sub.3-C.sub.7)-cycloalkyl,
(C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-- alkyl or
tri-(C.sub.1-C.sub.2)-alkylsilyl, by preference
(C.sub.1-C.sub.4)-alkyl;
[0158] R.sup.27 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl or (C.sub.3-C.sub.7)-cycloalkyl, by
preference hydrogen or (C.sub.1-C.sub.4)-alkyl, and
[0159] R.sup.26 is hydrogen or (C.sub.1-C.sub.4)-alkyl.
[0160] Also especially preferred are herbicidal compositions
comprising safeners of the formula (II) wherein the symbols and
indices have the following definitions:
[0161] W is (W2);
[0162] R.sup.17 is hydrogen, halogen or
(C.sub.1-C.sub.2)-haloalkyl;
[0163] n' is 1, 2 or 3, where (R.sup.17).sub.n' is by preference
2,4-Cl.sub.2;
[0164] R.sup.18 is a radical of the formula OR.sup.24;
[0165] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-hydroxyalkyl,
(C.sub.3-C.sub.7)-cycloalkyl,
(C.sub.1-C.sub.4-alkoxy)-C.sub.1-C.sub.4-al- kyl or
tri-(C.sub.1-C.sub.2)-alkyl-silyl, by preference
(C.sub.1-C.sub.4)-alkyl, and
[0166] R.sup.27 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.7)-cycloalkyl or
phenyl, by preference hydrogen or (C.sub.1-C.sub.4)-alkyl.
[0167] Also especially preferred are herbicidal compositions
comprising safeners of the formula (II) wherein the symbols and
indices have the following definitions:
[0168] W is (W3);
[0169] R.sup.17 is hydrogen, halogen or
(C.sub.1-C.sub.2)-haloalkyl;
[0170] n' is 1, 2 or 3, where (R.sup.17).sub.n is by preference
2,4-Cl.sub.2;
[0171] R.sup.18 is a radical of the formula OR.sup.24;
[0172] R.sup.24 is hydrogen, (C.sub.1-C.sub.8)-alkyl,
(C.sub.3-C.sub.7)-cycloalkyl, by preference
(C.sub.1-C.sub.4)-alkyl, and
[0173] R.sup.28 is (C.sub.1-C.sub.8)-alkyl or
(C.sub.1-C.sub.4)-haloalkyl, by preference C.sub.1-haloalkyl.
[0174] Also especially preferred are herbicidal compositions
comprising safeners of the formula (II) wherein the symbols and
indices have the following definitions:
[0175] W is (W4);
[0176] R.sup.17 is hydrogen, halogen, nitro,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.2)-haloalkyl, by preference
CF.sub.3;
[0177] n' is 1, 2 or 3;
[0178] m' is 0 or 1;
[0179] R.sup.18 is a radical of the formula OR.sup.24;
[0180] R.sup.24 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
carboxy-(C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl-(C.sub.- 11-C.sub.4)-alkyl, by
preference (C.sub.1-C.sub.4)-alkoxy-CO--CH.sub.2--,
(C.sub.1-C.sub.4)-alkoxy-CO--C(CH.sub.3)(H)--, HO--CO--CH.sub.2--
or HO--CO--C(CH.sub.3)(H)--, and
[0181] R.sup.29 is hydrogen, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.3-C.sub.7)-cycloalkyl or phenyl
which is unsubstituted or substituted by one or more of the
radicals selected from the group consisting of halogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl, nitro, cyano
and (C.sub.1-C.sub.4)-alkoxy.
[0182] The following groups of compounds are especially suitable
for use as safeners for the herbicidally active substances of the
formula (I):
[0183] a) Compounds of the dichlorophenylpyrazoline-3-carboxylic
acid type (i.e. of the formula (II) where W=W1 and
(R.sup.17).sub.n'=2,4-Cl.sub.2), by preference compounds such as
ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycar-
bonyl)-5-methyl-2-pyrazoline-3-carboxylate (II-1), and related
compounds as they are described in WO-A 91/07874;
[0184] b) dichlorophenylpyrazolecarboxylic acid derivatives (i.e.
of the formula (II) where W=(W2) and
(R.sup.17).sub.n'=2,4-Cl.sub.2), by preference compounds such as
ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazol- e-3-carboxylate
(11-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-
-carboxylate (II-3), ethyl
1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyr-
azole-3-carboxylate (II-4), ethyl
1-(2,4-dichlorophenyl)-5-phenylpyrazole-- 3-carboxylate (II-5) and
related compounds as they are described in EP-A-0 333 131 and
EP-A-0 269 806.
[0185] c) Compounds of the triazolecarboxylic acid type (i.e. of
the formula (II) where W=(W3) and (R.sup.17).sub.n'=2,4-Cl.sub.2),
by preference compounds such as fenchlorazol, i.e. ethyl
1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylat-
e (II-6), and related compounds (see EP-A-0 174 562 and EP-A-0 346
620);
[0186] d) compounds of the 5-benzyl- or
5-phenyl-2-isoxazoline-3-carboxyli- c acid type or the
5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (where W=(W4)),
by preference compounds such as ethyl
5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (II-7) or ethyl
5-phenyl-2-isoxazoline-3-carboxylate (II-8) and related compounds
as they are described in WO-A-91/08202, or ethyl
5,5-diphenyl-2-isoxazoline-3-car- boxylate (II-9) or n-propyl
5,5-diphenyl-2-isoxazoline-3-carboxylate (II-10) or ethyl
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (II-11), as
they are described in WO-A-95/07897.
[0187] e) Compounds of the 8-quinolinoxyacetic acid type, for
example those of the formula (III) where (R.sup.19).sub.n'=5-Cl or
hydrogen, R.sup.20=OR.sup.24 and T=CH.sub.2, by preference the
compounds
[0188] 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (III-1,
cloquintocet-mexyl),
[0189] 1,3-dimethylbut-1-yl (5-chloro-8-quinolinoxy)acetate
(III-2),
[0190] 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (III-3),
[0191] 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate
(III-4),
[0192] ethyl (5-chloro-8-quinolinoxy)acetate (III-5),
[0193] methyl (5-chloro-8-quinolinoxy)acetate (III-6),
[0194] allyl (5-chloro-8-quinolinoxy)acetate (III-7),
[0195] 2-(2-propylideniminoxy)-1-ethyl
(5-chloro-8-quinolinoxy)acetate (III-8),
[0196] 2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (III-9)
[0197] and related compounds as they are described in EP-A-0 860
750, EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366.
[0198] f) Compounds of the (5-chloro-8-quinolinoxy)malonic acid
type, i.e. of the formula (III) where (R.sup.17).sub.n'=5-Cl,
R.sup.20=OR.sup.24, T=CH(COO-alkyl)-, by preference the compounds
diethyl (5-chloro-8-quinolinoxy)malonate, diallyl
(5-chloro-8-quinolinoxy)malonat- e, methyl ethyl
(5-chloro-8-quinolinoxy)malonate and related compounds as they are
described in EP-A-0 582 198.
[0199] g) Compounds of the dichloroacetamide type, i.e. of the
formula (IV), by preference:
[0200] N,N-diallyl-2,2-dichloroacetamide (dichlormid, from U.S.
Pat. No. 4,137,070),
[0201] 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine
(benoxacor, from EP 0 149 974),
[0202] N1,N2-diallyl-N-2-dichloroacetylglycinamide (DKA-24, from HU
2143821),
[0203] 4-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (AD-67),
[0204]
2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide
(PPG-1292),
[0205] 3-dichloroacetyl-2,2,5-trimethyloxazolidine,
[0206] 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,
[0207] 3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine,
[0208] 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine
(furilazole, MON 13900),
[0209]
1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6
(2H)-one (dicyclonon, BAS 145138),
[0210] h) compounds of group B(b), by preference
[0211] 1,8-naphthalic anhydride,
[0212] methyl diphenylmethoxyacetate,
[0213] cyanomethoxyimino(phenyl)acetonitrile (cyometrinil),
[0214] 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile
(oxabetrinil),
[0215] 4'-chloro-2,2,2-trifluoroacetophenone
O-1,3-dioxolan-2-ylmethyl oxime (fluxofenim),
[0216] 4,6-dichloro-2-phenylpyrimidine (fenclorim),
[0217] benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate
(flurazole),
[0218] 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),
[0219] N-(4-methylphenyl)-N'-(1-methyl-1-phenylethyl)urea
(dymron),
[0220] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,
[0221]
1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,
[0222]
1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,
[0223] 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,
[0224] (2,4-dichlorophenoxy)acetic acid (2,4-D),
[0225] (4-chlorophenoxy)acetic acid,
[0226] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
[0227] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
[0228] (4-chloro-o-tolyloxy)acetic acid (MCPA),
[0229] 4-(4-chloro-o-tolyloxy)butyric acid,
[0230] 4-(4-chlorophenoxy)butyric acid,
[0231] 3,6-dichloro-2-methoxybenzoic acid (dicamba),
[0232] 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate
(lactidichlor),
[0233] and their salts and esters, by preference
(C.sub.1-C.sub.8).
[0234] Further preferred safeners are compounds of the formula (V)
or salts thereof in which
[0235] R.sup.30 is hydrogen, (C.sub.1-C.sub.6)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl, where each of the last-mentioned 2
radicals is unsubstituted or substituted by one or more
substituents selected from the group consisting of halogen,
(C.sub.1-C.sub.4)-alkoxy, halo-(C.sub.1-C.sub.6)-alkoxy and
(C.sub.1-C.sub.4)-alkylthio and, in the case of cyclic radicals,
also (C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl,
[0236] R.sup.31 is hydrogen;
[0237] R.sup.32 is halogen, halo-(C.sub.1-C.sub.4)-alkyl,
halo-(C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl or
(C.sub.1-C.sub.4)-alkylcarbonyl, by preference halogen,
(C.sub.1-C.sub.4)-haloalkyl such as trifluoromethyl,
(C.sub.1-C.sub.4)-alkoxy, halo-(C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxycarbonyl or
(C.sub.1-C.sub.4)-alkylsulfonyl,
[0238] R.sup.33 is hydrogen;
[0239] R.sup.34 is halogen, (C.sub.1-C.sub.4)-alkyl,
halo-(C.sub.1-C.sub.4)-alkyl, halo-(C.sub.1-C.sub.4)-alkoxy,
(C.sub.3-C.sub.6)-cycloalkyl, phenyl, (C.sub.1-C.sub.4)-alkoxy,
cyano, (C.sub.1-C.sub.4)-alkylthio,
(C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl or
(C.sub.1-C.sub.4)-alkylcarbonyl, by preference halogen,
(C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-haloalkyl such as
trifluoromethyl, halo-(C.sub.1-C.sub.4)-alkoxy,
(C.sub.1-C.sub.4)-alkoxy or (C.sub.1-C.sub.4)-alkylthio,
[0240] n is 0, 1 or 2and
[0241] m is 1 or 2.
[0242] Also preferred are safeners of the formula (VI) in which
[0243] X.sup.3 is CH;
[0244] R.sup.35 is hydrogen, (C.sub.1-C.sub.6)-alkyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.2-C.sub.6)-alkenyl,
(C.sub.5-C.sub.6)-cycloalkenyl, phenyl or 3- to 6-membered
heterocyclyl having up to three heteroatoms selected from the group
consisting of nitrogen, oxygen and sulfur, the six last-mentioned
radicals optionally being substituted by one or more identical or
different substituents selected from the group consisting of
halogen, (C.sub.1-C.sub.6)-alkoxy, (C.sub.1-C.sub.6)-haloalkoxy,
(C.sub.1-C.sub.2)-alkylsulfinyl, (C.sub.1-C.sub.2)-alkylsulfonyl,
(C.sub.3-C.sub.6)-cycloalkyl, (C.sub.1-C.sub.4)-alkoxycarbonyl,
(C.sub.1-C.sub.4)-alkylcarbonyl and phenyl and in the case of
cyclic radicals, also (C.sub.1-C.sub.4)-alkyl and
(C.sub.1-C.sub.4)-haloalkyl;
[0245] R.sup.36 is hydrogen, (C.sub.1-C.sub.6)-alkyl,
(C.sub.2-C.sub.6)-alkenyl, (C.sub.2-C.sub.6)-alkynyl, the three
last-mentioned radicals optionally being substituted by one or more
identical or different substituents selected from the group
consisting of halogen, hydroxyl, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy and (C.sub.1-C.sub.4)-alkylthio;
[0246] R.sup.37 is halogen, (C.sub.1-C.sub.4)-haloalkyl,
(C.sub.1-C.sub.4)-haloalkoxy, nitro, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-alkoxy, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl or
(C.sub.1-C.sub.4)-alkylcarbonyl;
[0247] R.sup.38 is hydrogen;
[0248] R.sup.39 is halogen, nitro, (C.sub.1-C.sub.4)-alkyl,
(C.sub.1-C.sub.4)-haloalkyl, (C.sub.1-C.sub.4)-haloalkoxy,
(C.sub.3-C.sub.6)-cycloalkyl, phenyl, (C.sub.1-C.sub.4)-alkoxy,
cyano, (C.sub.1-C.sub.4)-alkylthio,
(C.sub.1-C.sub.4)-alkylsulfinyl, (C.sub.1-C.sub.4)-alkylsulfonyl,
(C.sub.1-C.sub.4)-alkoxycarbonyl or
(C.sub.1-C.sub.4)-alkylcarbonyl;
[0249] r is 0, 1 or 2and
[0250] q is 1 or 2.
[0251] Further particularly preferred safeners are compounds of the
formula (VII), in which
[0252] R.sup.40 is trifluoromethyl,
[0253] R.sup.41 is hydrogen, and
[0254] R.sup.42 is hydrogen, methyl or ethyl.
[0255] The compounds cited here as safeners (antidotes) reduce or
prevent phytotoxic effects which may occur when using the
herbicidally active substances of the formula (I) in crops of
useful plants without substantially affecting the activity of these
herbicidally active substances against weed plants. This allows the
field of application of conventional crop protection products to be
widened quite considerably and to be extended to, for example,
crops such as wheat, barley, corn, and sugar cane in which use of
the herbicides was hitherto impossible, or of only limited
possibility, that is to say at low rates and with a restricted
spectrum.
[0256] The herbicidally active substances and the abovementioned
safeners can be applied together (as a readymix or by the tank mix
method) or in succession in any desired sequence. The weight ratio
of safener to herbicidally active substance may vary within wide
limits and is preferably within the range from 1:100 to 100:1, in
particular from 1:10 to 10:1. The optimum amounts of herbicidally
active substance and safener in each case depend on the type of the
herbicidally active substance used or on the safener used and on
the species of the plant stand to be treated and can be determined
in each individual case by simple, routine preliminary
experiments.
[0257] Main fields of application for the combinations according to
the invention are, in particular, corn, sugar cane and cereal crops
for example wheat, rye, barley, oats, rice, sorghum, but also
cotton and soybeans, preferably sugar cane, cereals, rice and
corn.
[0258] Depending on their properties, the safeners employed in
accordance with the invention can be used for pretreating the seeds
of a crop plant (seed dressing), or be incorporated into the seed
furrows prior to sowing or applied together with the herbicide
before or after plant emergence. The preemergence treatment
includes both the treatment of the area under cultivation prior to
sowing and the treatment of the areas under cultivation where the
seeds have been planted but the plants have not yet emerged. Joint
application with the herbicide is preferred. To this end, tank
mixes or readymixes can be employed.
[0259] The application rates of safener required may vary within
wide limits depending on the indication and the herbicidally active
substance used and are generally in the range of from 0.001 to 5
kg, preferably 0.005 to 0.5 kg, of active substance per
hectare.
[0260] The present invention therefore also provides a method of
protecting crop plants from phytotoxic side effects of herbicides
of the formula (I), which comprises applying an antidote-active
amount of a compound of the formula (II), (III), (IV), (V), (VI),
(VII) and/or from group (b) to the plants, the seeds of the plants
or the area under cultivation, before, after or simultaneously with
the herbicidally active substance A of the formula (I).
[0261] The herbicide/safener combination according to the invention
may also be employed for controlling weed plants in crops of
genetically engineered plants which are either known or still to be
developed. As a rule, the transgenic plants are distinguished by
particular, advantageous properties, for example by resistances to
certain crop protection agents, resistances to plant diseases or
pathogens causing plant diseases such as particular insects or
microorganisms such as fungi, bacteria or viruses. Other particular
properties relate, for example, to the harvested material in terms
of quantity, quality, storing properties, composition and specific
constituents. Thus, transgenic plants are known which have an
increased starch content or an altered starch quality, or those
where the harvested material has a different fatty acid
composition.
[0262] The use of the combinations according to the invention is
preferred in economically important transgenic crops of useful
plants and ornamentals, for example cereals such as wheat, barley,
rye, oats, millet, rice, cassaya and corn or else crops of sugar
beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and
other types of vegetables.
[0263] When the combinations according to the invention are
employed in transgenic crops, effects on weed plants to be observed
in other crops are frequently accompanied by effects which are
specific for application in the transgenic crop in question, for
example an altered or specifically widened weed spectrum which can
be controlled, altered application rates which may be used,
preferably good compatibility with the herbicides to which the
transgenic crop is resistant, and altered growth and yield of the
transgenic crop plants.
[0264] The invention therefore also provides for the use of the
combination according to the invention for controlling weed plants
in transgenic crop plants.
[0265] The safeners of the formulae (III)-(VII) and of group (b)
and their combinations with one or more of the abovementioned
herbicidally active substances of the formula (I) can be formulated
in various ways, depending on the biological and/or
chemico-physical parameters specified. Examples of suitable
formulations which are possible are: wettable powders (WP),
emulsifiable concentrates (EC), water-soluble powders (SP),
water-soluble concentrates (SL), concentrated emulsions (BW) such
as oil-in-water and water-in-oil emulsions, sprayable solutions or
emulsions, capsule suspensions (CS), oil- or water-based
dispersions (SC), suspoemulsions, suspension concentrates, dusts
(DP), oil-miscible solutions (OL), seed dressing products, granules
(GR) in the form of microgranules, spray granules, coated granules
and adsorption granules, granules for soil application or
broadcasting, water-soluble granules (SG), water-dispersible
granules (WG), ULV formulations, microcapsules and waxes.
[0266] These individual formulation types are known in principle
and described, for example, in: Winnacker-Kuchler, "Chemische
Technologie" [Chemical Engineering], Volume 7, C. Hauser Verlag
Munich, 4.sup.th Edition 1986; Wade van Valkenburg, "Pesticide
Formulations", Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying
Handbook", 3.sup.rd Ed. 1979, G. Goodwin Ltd. London.
[0267] The formulation auxiliaries which may be required, such as
inert materials, surfactants, solvents and other additives are also
known and described, for example, in: Watkins, "Handbook of
Insecticide Dust Diluents and Carriers", 2.sup.nd Ed., Darland
Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid
Chemistry", 2.sup.nd Ed., J. Wiley & Sons, N.Y.; C. Marsden,
"Solvents Guide", 2.sup.nd Ed., Interscience, N.Y. 1963;
McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp.,
Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active
Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,
"Grenzflchenaktive thylenoxidaddukte" [Surface-active Ethylene
Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler, "Chemische Technologie" [Chemical Engineering],
Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.
[0268] Based on these formulations, it is also possible to prepare
combinations with other substances which act as crop protection
agents, such as insecticides, acaricides, herbicides, fungicides,
and also with safeners, fertilizers and/or growth regulators, for
example in the form of a readymix or as a tank mix.
[0269] Wettable powders are preparations which are uniformly
dispersible in water and which, besides the active substance, also
comprise ionic and/or nonionic surfactants (wetting agents,
dispersants), for example polyoxyethylated alkylphenols,
polyoxyethylated fatty alcohols, polyoxyethylated fatty amines,
fatty alcohol polyglycol ether sulfates, alkanesulfonates,
alkylbenzenesulfonates, sodium lignosulfonate, sodium
2,2'-dinaphthylmethane-6,6'-disulfonate, sodium
dibutylnaphthalenesulfona- te, or else sodium
oleoylmethyltaurinate, in addition to a diluent or inert substance.
To prepare the wettable powders, the herbicidally active substances
are ground finely, for example in customary apparatus such as
hammer mills, blower mills and air-jet mills, and they are
simultaneously or subsequently mixed with the formulation
auxiliaries.
[0270] Emulsifiable concentrates are prepared, for example, by
dissolving the active substance in an organic solvent such as
butanol, cyclohexanone, DMF, or else higher-boiling hydrocarbons
such as saturated or unsaturated aliphatics or alicycles, aromatics
or mixtures of the organic solvents with the addition of one or
more ionic and/or nonionic surfactants (emulsifiers). Examples of
substances which can be used as emulsifiers are: calcium
alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or
nonionic emulsifiers such as fatty acid polyglycol esters,
alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers,
propylene oxide/ethylene oxide condensates, alkyl polyethers,
sorbitan esters, such as sorbitan fatty acid esters or
polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan
fatty acid esters. Dusts are generally obtained by grinding the
active substance with finely divided solid substances, for example
talc, natural clays such as kaolin, bentonite and pyrophyllite, or
diatomaceous earth.
[0271] Suspension concentrates can be water- or oil-based. They can
be prepared, for example, by wet-grinding using commercially
available bead mills with or without addition of surfactants, for
example those which have already been mentioned above in the case
of the other formulation types.
[0272] Emulsions, for example oil-in-water emulsions (EW), can be
prepared, for example, by means of stirrers, colloid mills and/or
static mixers using aqueous organic solvents in the presence or
absence of surfactants which have already been mentioned above, for
example, in the case of the other formulation types.
[0273] Granules can be prepared either by spraying the active
substance onto adsorptive, granulated inert material or by applying
active substance concentrates to the surface of carriers such as
sand, kaolinites or granulated inert material with the aid of
binders, for example polyvinyl alcohol, sodium polyacrylate or else
mineral oils. Suitable active substances can also be granulated in
the manner which is conventional for the preparation of fertilizer
granules, if desired as a mixture with fertilizers. As a rule,
water-dispersible granules are prepared by the customary processes
such as spray-drying, fluidized-bed granulation, disk granulation,
mixing with high-speed mixers and extrusion without solid inert
material.
[0274] For the preparation of disk, fluidized-bed, extruder and
spray granules see, for example, "Spray-Drying Handbook" 3.sup.rd
ed. 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration",
Chemical and Engineering 1967, pages 147 et seq.; "Perry's Chemical
Engineer's Handbook", 5.sup.th Ed., McGraw-Hill, New York 1973, p.
8-57.
[0275] For further details on the formulation of crop protection
products see, for example, G. C. Klingman, "Weed Control as a
Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96
and J. D. Freyer, S. A. Evans, "Weed Control Handbook", 5.sup.th
Ed., Blackwell Scientific Publications, Oxford, 1968, pages
101-103.
[0276] As a rule, the agrochemical formulations comprise 0.1 to 99%
by weight, in particular 0.1 to 95% by weight, of active substances
of the formulae (II)-(VII) and/or (b) or of the herbicide/antidote
mixture of active substances (I) and (II)-(VII) and/or (b) and 1 to
99.9% by weight, in particular 5 to 99.8% by weight, of a solid or
liquid additive and 0 to 25% by weight, in particular 0.1 to 25% by
weight, of a surfactant.
[0277] In wettable powders, the active substance concentration is,
for example, approximately 10 to 90% by weight, the remainder to
100% by weight being composed of customary formulation components.
In the case of emulsifiable concentrates, the active substance
concentration is approximately 1 to 80% by weight. Formulations in
the form of dusts comprise approximately 1 to 20% by weight of
active substances, sprayable solutions approximately 0.2 to 20% by
weight of active substances. In the case of granules such as
water-dispersible granules, the active substance content depends
partly on whether the active compound is in liquid or solid form.
The active substance content of the water-dispersible granules is,
as a rule, between 10 and 90% by weight.
[0278] Besides this, the abovementioned formulations of active
substances comprise, if appropriate, the adhesives, wetters,
dispersants, emulsifiers, penetrants, preservatives, antifreeze
agents, solvents, fillers, carriers, colorants, antifoams,
evaporation inhibitors and pH and viscosity regulators which are
customary in each case.
[0279] Co-components which can be used for the mixtures of
herbicides and safeners according to the invention in mixed
formulations or in a tank mix are, for example, known active
substances as they are described, for example, in Weed Research 26,
441-445 (1986), or "The Pesticide Manual", 10.sup.th edition, The
British Crop Protection Council, 1994, and in the literature cited
therein. Herbicides which are known from the literature and which
can be combined with the mixtures according to the invention are,
for example, the following active substances (note: either the
common names in accordance with the International Organization for
Standardization (ISO) or the chemical names, if appropriate
together with the customary code number, of the compounds are
given):
[0280] acetochlor; acifluorfen; aclonifen; AKH 7088, i.e.
[[[1-[5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrophenyl]-2-methoxyet-
hylidene]amino]oxy]acetic acid and its methyl ester; alachlor;
alloxydim; ametryn; amidosulfuron; amitrol; AMS, i.e. ammonium
sulfamate; anilofos; asulam; atrazin; azafenidine (DPX-R6447),
azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516H, i.e.
5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-- one; benazolin;
benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone;
benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;
bispyribac-sodium (KIH-2023), bromacil; bromobutide; bromofenoxim;
bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos;
butenachlor; buthidazole; butralin; butroxydim (ICI-0500),
butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDM,
i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chloroallyl
diethyldithiocarbamate; chlomethoxyfen; chloramben;
chloransulam-methyl (XDE-565), chlorazifop-butyl, chlorbromuron;
chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon;
chlorimuron-ethyl; chlornitrofen; chlorotoluron; chloroxuron;
chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid;
cinidon-ethyl, cinmethylin; cinosulfuron; clefoxydim, clethodim;
clodinafop and its ester derivatives (for example
clodinafop-propargyl); clomazone; clomeprop; cloproxydim;
clopyralid; cumyluron (JC 940); cyanazine; cycloate;
cyclosulfamuron (AC 014); cycloxydim; cycluron; cyhalofop and its
ester derivatives (for example butyl ester, DEH-1 12); cyperquat;
cyprazine; cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn;
di-allate; dicamba; dichlobenil; dichlorprop; diclofop and its
esters such as diclofop-methyl; diclosulam (XDE-564), diethatyl;
difenoxuron; difenzoquat; diflufenican; diflufenzopyr-sodium
(SAN-835H), dimefuron; dimethachlor; dimethametryn; dimethenamid
(SAN-582H); dimethazone, methyl 5-(4,6-dimethylpyrimidin-2-y-
l-carbamoylsulfamoyl)-1-(2-pyridyl)-pyrazole-4-carboxylate
(NC-330); clomazon; dimethipin; dimetrasulfuron, dinitramine;
dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr;
diuron; DNOC; eglinazine-ethyl; EL 177, i.e.
5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-- pyrazole-4-carboxamide;
endothal; epoprodan (MK-243), EPTC; esprocarb; ethalfluralin;
ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231,
i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5--
dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide; ethoxyfen
and its ester (for example ethyl ester, HN-252); ethoxysulfuron
(from EP 342569); etobenzanid (HW 52);
3-(4-ethoxy-6-ethyl-1,3,5-triazin-2-yl)-1-(2,3-dihyd-
ro-1,1-dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea (EP-A 079
683);
3-(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methy-
lbenzo[b]thiophene-7-sulfonyl)urea (EP-A 079 683); fenoprop;
fenoxan, fenoxaprop and fenoxaprop-P and their esters, for example
fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fentrazamide
(NBA-061); fenuron; flamprop-methyl; flazasulfuron; flufenacet
(BAY-FOE-5043), fluazifop and fluazifop-P, florasulam (DE-570) and
their esters, for example fluazifop-butyl and fluazifop-P-butyl;
fluazolate (Mon-48500), fluchloralin; flucarbazone-sodium;
flumetsulam; flumeturon; flumiclorac and its esters (for example
pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam
(KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil
(UBIC-4243); sodium flupyrsulfuron-methyl (DPX-KE459), fluridone;
flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl
(K1H-9201), fomesafen; fosamine; furyloxyfen; glufosinate;
glyphosate; halosafen; halosulfuron and its esters (for example
methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P
(.dbd.R-haloxyfop) and its esters; hexazinone;
imazamethabenz-methyl; imazamox (AC-299263), imazapyr; imazaquin
and salts such as the ammonium salt; imazethamethapyr; imazethapyr;
imazosulfuron; iodosulfuron (methyl
4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-
-triazin-2-yl)ureidosulfonyl]benzoate, sodium salt, WO 92/13845);
ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben;
isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB;
mecoprop; mefenacet; mefluidid; metamitron; metazachlor;
methabenzthiazuron; metham; methazole; methoxyphenone;
methyldymron; metabenzuron, methyl
2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methanesulfonamidomet-
hylbenzoate (WO 95/10507); methobenzuron; metobromuron;
metolachlor; S-metolachlor, metosulam (XRD 511); metoxuron;
metribuzin; metsulfuron-methyl; MH; molinate; monalide;
monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e.
6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine;
MT 5950, i.e.
N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide;
N,N-dimethyl-2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-formylam-
inobenzamide (WO 95/01344); naproanilide; napropamide; naptalam; NC
310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole;
neburon; nicosulfuron; nipyraclofen; nitralin; nitrofen;
nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl
(RP-020630); oxadiazon; oxaziclomefone (MY-100), oxyfluorfen;
oxasulfuron (CGA-277476), paraquat; pebulate; pendimethalin;
pentoxazone (KPP-314), perfluidone; phenisopham; phenmedipham;
picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor;
primisulfuron-methyl; pracarbazone-sodium; procyazine; prodiamine;
profluralin; proglinazine-ethyl; prometon; prometryn; propachlor;
propanil; propaquizafop and its esters; propazine; propham;
propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron
(CGA-152005); prynachlor; pyraflufen-ethyl (ET-751), pyrazon;
pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim, pyridafol;
pyridate; pyriminobac-methyl (KIH-6127), pyrithiobac (KIH-2031);
pyroxofop and its esters (for example propargyl ester); quinclorac;
quinmerac; quinofop and its ester derivatives, quizalofop and
quizalofop-P and their ester derivatives, for example
quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron;
rimsulfuron (DPX-E 9636); S 275, i.e.
2-[4-chloro-2-fluoro-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro
-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn;
SN 106279, i.e.
2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]o-
xy]propanoic acid and its methyl ester; sulfentrazon (FMC-97285,
F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224);
sulfosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebuthiuron;
tepraloxydim (BAS-620H), terbacil; terbucarb; terbuchlor;
terbumeton; terbuthylazine; terbutryn; TFH 450, i.e.
N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-
-1H-1,2,4-triazole-1-carboxamide; thenylchlor (NSK-850);
thiazafluron; thiazopyr (Mon-1 3200); thidiazimin (SN-1 24085);
thifensulfuron-methyl; thiobencarb; thiocarbazil; tralkoxydim;
tri-allate; triasulfuron; triaziflam (DH-1105); triazofenamide;
tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin;
triflusulfuron and esters (for example methyl ester, DPX-66037);
trimeturon; tsitodef; vernolate; WL 110547, i.e.
5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509;
D-489; LS 82-556; KPP-300; KPP-421, MT-146, NC-324; KH-218;
DPX-N8189; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001.
[0281] For use, the formulations which are in commercially
available form are, if desired, diluted in the customary manner,
for example using water in the case of wettable powders,
emulsifiable concentrates, dispersions and water-dispersible
granules. Preparations in the form of dusts, soil granules,
granules for broadcasting and sprayable solutions are usually not
diluted any further with other inert substances prior to use.
[0282] The necessary application rate of the herbicides of the
formula (I) varies with the external conditions such as, inter
alia, temperature, humidity, and the nature of the herbicide used.
It may be varied within wide limits, for example between 0.001 and
10.0 kg/ha or more of active substance, but it is preferably
between 0.005 and 5 kg/ha.
[0283] The examples which follow serve to illustrate the
invention:
[0284] A. Formulation Examples
[0285] a) A dust is obtained by mixing 10 parts by weight of a
compound of the formula (II)-(VII) and/or from group (b) or of an
active substance mixture of a herbicidally active substance of the
formula (I) and a safener of the formula (II)-(VII) and/or from
group (b) and 90 parts by weight of talc as inert substance and
comminuting the mixture in a hammer mill.
[0286] b) A wettable powder which is readily dispersible in water
is obtained by mixing 25 parts by weight of a compound of the
formula (II), (III), (IV) and/or from group (b) or of an active
substance mixture of a herbicidally active substance of the formula
(I) and a safener of the formula (II), (III), (IV) and/or from
group (b), 64 parts by weight of kaolin-containing quartz as inert
substance, 10 parts by weight of potassium lignosulfonate and 1
part by weight of sodium oleoylmethyltaurinate as wetter and
dispersant, and grinding the mixture in a pinned-disk mill.
[0287] c) A dispersion concentrate which is readily dispersible in
water is obtained by mixing 20 parts by weight of a compound of the
formula (II)-(VII) and/or from group (b) or of an active substance
mixture of a herbicidally active substance of the formula (I) and a
safener of the formula (II)-(VII) and/or from group (b), 6 parts by
weight of alkylphenol polyglycol ether (.RTM.Triton X 207), 3 parts
by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by
weight of paraffinic mineral oil (boiling range, for example,
approx. 255 to above 277.degree. C.) and grinding the mixture in a
ball mill to a fineness of below 5 microns.
[0288] d) An emulsifiable concentrate is obtained from 15 parts by
weight of a compound of the formula (II)-(VII) and/or from group
(b) or of an active substance mixture of a herbicidally active
substance of the formula (I) and a safener of the formula
(II)-(VII) and/or from group (b), 75 parts by weight of
cyclohexanone as solvent and 10 parts by weight of ethoxylated
nonylphenol as emulsifier.
1 e) Water-dispersible granules are obtained by mixing 75 parts by
weight of a compound of the formula (II)-(VII) and/or from group
(b) or of an active substance mixture of a herbicidally active
substance of the formula (I) and a safener of the formula
(II)-(VII) and/or from group (b) 10 parts by weight of calcium
lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts
by weight of polyvinyl alcohol and 7 parts by weight of kaolin,
grinding the mixture on a pinned-disk mill and granulating the
powder in a fluidized bed by spraying on water as granulation
liquid. f) Water-dispersible granules are also obtained by
homogenizing and precomminuting, in a colloid mill, 25 part(s) by
weight of a compound of the formula (II)-(VII) and/or from groups
(b) or of an active substance mixture of a herbicidally active
substance of the formula (I) and a safener of the formula
(II)-(VII) and/or from group (b) 5 part(s) by weight of sodium
2,2'-dinaphthylmethane-6,6'- disulfonate 2 part(s) by weight of
sodium oleoylmethyltaurinate, 1 part(s) by weight of polyvinyl
alcohol, 17 part(s) by weight of calcium carbonate and 50 part(s)
by weight of water, subsequently grinding the mixture on a bead
mill and atomizing and drying the resulting suspension in a spray
tower by means of a single-substance nozzle.
BIOLOGICAL EXAMPLES
[0289] 1. Damage Scoring
[0290] The damage to the plants is evaluated visually in comparison
with control plants, according to a scale from 0-100%:
[0291] 0%=no perceptible action in comparison with the untreated
plant,
[0292] 100%=treated plant dies.
[0293] 2. Herbicide Action and Safener Action Preemergence
[0294] Seeds of monocotyledonous and dicotyledonous broadleaf weed
plants and of crop plants are placed in sandy loam and plastic pots
of 9 cm in diameter and are covered with soil. Alternatively, for
the test under conditions for paddy rice, broadleaf weeds which
occur in rice growing are cultivated in waterlog soil, the amount
of water introduced into the pots being such that the water comes
up to the soil surface or several millimeters above it. The
herbicide/safener active substance combinations of the invention,
formulated in the form of emulsifiable concentrates, and, in
parallel trials, the correspondingly formulated individual active
substances, are then applied to the surface of the covering earth
or, in the case of rice, poured into the irrigation water in the
form of emulsions, at a water application rate of 300 l/ha
(converted), at different concentrations.
[0295] Following treatment, the pots are placed in a greenhouse and
are kept under good growth conditions. Visual scoring of the plant
and/or emergence damage takes place after the trial plants have
emerged, after a trial period of 34 weeks, in comparison to
untreated controls. As the trials show, the herbicidal compositions
of the invention have a good preemergence herbicidal action against
a broad spectrum of gramineous and broadleaf weeds, with
substantial reduction--that is, from around 50% up to 100% less
herbicide damage--in damage to crop plants such as corn, rice,
wheat or barley or other cereals in comparison with the use of the
individual herbicides without safeners.
[0296] 3. Herbicide Action and Safener Action Postemergence
[0297] Seeds of monocotyledonous and dicotyledenous broadleaf weed
plants and of crop plants are placed in sandy loam and plastic
pots, colored with soil and grown in a greenhouse under good growth
conditions. Alternatively, for the test under conditions for paddy
rice, broadleaf weeds that occur in rice growing, and rice, are
cultivated in pots in which water stands up to 2 cm above the soil
surface, and are cultivated during the growth phase. About three
weeks after sowing, the trial plants are treated at the three-leaf
stage. The herbicide/safener active substance combinations of the
invention, formulated as emulsifable or concentrates, and, in
parallel trials, the correspondingly formulated individual active
substances are sprayed on the green parts of the plants at
different concentrations with a water application rate of 300 l/ha
(converted) and, after the trial plants have stood in the
greenhouse for 3 weeks under optimum growth conditions, the action
of the preparations is scored visually in comparison with untreated
controls. In the case of rice or broadleaf weeds which occur in
rice growing, the active substances are also introduced directly
into the irrigation water (application in analogy to granular
application, as it is known) or on plants and sprayed into the
irrigation water. In the case of field trials, seeds of
monocotyledonous and dicotyledonous broadleaf weed plants and of
crop plants were placed in sandy loam, covered with earth and
grown. Further treatment was as described above. Evaluation in the
case took place two weeks after the treatment with herbicide and/or
safener. In the case of the trials with sugar cane, evaluation was
carried out after 63 days. The experiments show that the herbicidal
compositions of the invention exhibit a good postemergence
herbicidal action against a broad spectrum of gramineous and
broadleaf weeds, with substantial reduction--i.e., around 50% up to
100% less herbicide damage--in damage to crop plants such as sugar
cane, corn, rice, wheat or barley or other cereals in comparison
with the use of the individual herbicides without safeners.
[0298] Table 1 specifies the herbicides used, and table 2 the
safeners. Tables 3 to 7 indicate the percentage by which the damage
in corn, sugar cane, rice, wheat or barley, respectively, caused by
a herbicide is lessened by simultaneous use of the safener.
2TABLE 1 Herbicides No. Structure H1 7 H2 8 H3 9 H4 10 H5 11 H6 12
H7 13 H8 14
[0299]
3TABLE 2 Safeners No. Structure S1 15 S2 16 S3 17 S4 18 S5 19 S6 20
S7 21 S8 22 S9 23 S10 24
[0300]
4TABLE 3 Postemergence field trials, corn Compound No. Rate [g/ha]
Reduction in damage to Herbicide Safener Herbicide Safener corn
from using safener H1 S1 200 + 200 54% H1 S7 400 + 100 50% H2 S1
100 + 100 100% H2 S1 200 + 100 96% H2 S7 80 + 80 100% H2 S8 80 + 80
100% H2 S9 80 + 80 100% H2 S10 80 + 80 100% H3 S1 150 + 150 84% H4
S1 150 + 150 89% H5 S1 150 + 150 100% H6 S1 150 + 150 100% H7 S1
150 + 150 100% H8 S1 150 + 150 83%
[0301]
5TABLE 4 Postemergence field trials, sugar cane Reduction in
Compound No. Rate [g/ha] damage to sugar cane Herbicide Safener
Herbicide Safener from using safener H2 S1 200 + 200 60%
[0302]
6TABLE 5 Postemergence greenhouse trials, rice Reduction in
Compound No. Rate [g/ha] damage to rice Herbicide Safener Herbicide
Safener from using safener H1 S1 100 + 200 78% H1 S3 120 + 600 68%
H2 S2 200 + 600 63% H8 S1 200 + 200 71%
[0303]
7TABLE 6 Postemergence greenhouse trials, wheat Reduction in
Compound No. Rate [g/ha] damage to wheat Herbicide Safener
Herbicide Safener from using safener H1 S4 20 + 80 21% H1 S5 20 +
80 29% H2 S4 100 + 100 60% H2 S5 20 + 20 71% H2 S5 100 + 100 70% H2
S6 60 + 60 50%
[0304]
8TABLE 7 Postemergence greenhouse trials, barley Reduction in
Compound No. Rate [g/ha] damage to barley Herbicide Safener
Herbicide Safener from using safener H2 S5 180 + 180 100% H2 S5 100
+ 100 100% H2 S6 20 + 80 75%
[0305] In table 8, following the working examples, the seed was
first treated with safener and, after sowing and emergence, the
plant was then treated with herbicide. Here again, a marked
reduction in the damage caused by the herbicide is evident in
comparison to the seed which was not treated with safener. The
amount of safener indicated is based on the amount of seed.
9TABLE 8 Postemergence field trials following seed treatment, corn
Reduction in Compound No. Rate [g/ha] Rate [g/ha] damage to corn
Herbicide Safener Herbicide Safener from using safener H2 S1 80 0.1
90% H2 S3 80 0.1 84% H2 S7 80 0.01 84% H2 S8 80 0.05 87%
* * * * *